TW202125889A - Advanced lithium (li) ion and lithium sulfur (li s) batteries - Google Patents

Abstract

This disclosure provides a lithium (Li) ion battery that includes an anode, a cathode positioned opposite to the anode, a porous separator positioned between the anode and the cathode, and a liquid electrolyte in contact with the anode and the cathode. The anode includes an electrically conductive substrate. A first film is deposited on the electrically conductive substrate. The first film includes a first concentration of carbon particles in contact with each other and defines a first electrical conductivity for the first film. Each of the carbon particles includes a plurality of aggregates formed of few layer graphene sheets. The plurality of aggregates form a porous structure configured to undergo a lithiation, which can include any one or more of an intercalation operation or a plating operation. The anode and the cathode can include an electroactive material. The porous structure can provide conduction between the few layer graphene sheets.

Description

先進鋰離子及鋰硫電池Advanced lithium-ion and lithium-sulfur batteries

發明領域Field of invention

本揭露內容大體上關於產生以碳為主之粒子且更明確而言關於將所產生之以碳為主之粒子併入電池電極中。The present disclosure generally relates to the generation of carbon-based particles and, more specifically, the incorporation of the generated carbon-based particles into battery electrodes.

發明背景Background of the invention

技術進步已使得消費者能夠在許多新型應用中使用電子裝置，此情況在先前不具可能性。該等裝置已變得常見，許多該等裝置依賴於電池供應之電力且繼續愈來愈普及。電池-特別而言諸如可充電電池之二次電池已藉由允許可攜性及便利持續裝置使用而作為通用方案出現，滿足相關電力消耗需求。Technological advances have enabled consumers to use electronic devices in many new applications, which was previously impossible. These devices have become commonplace, and many of these devices rely on battery-supplied power and continue to grow in popularity. Batteries-In particular, secondary batteries such as rechargeable batteries have emerged as a general solution by allowing portability and convenient continuous device use to meet related power consumption requirements.

與可充電電池效能相關之挑戰存留，特別而言關於壽命及循環特性之挑戰因此吸引鋰離子(以簡短形式稱為Li離子)技術之持續創新。習知地，間夾Li化合物可用作與陽極處之石墨配對之陰極處之形成材料。與其他電池類型形成對比，Li離子電池已由於其相對高能量密度而被尋求在可攜電子裝置中之使用且限於無記憶效應，諸如在涉及局部放電及相對低自放電之多個充電-放電循環內損失其儲存電荷之能力之傳統鎳-鎘及鎳-金屬氫化物可充電電池所遇到的記憶效應。因此，Li離子電池提供許多在諸如非可充電Li電池之一次Li電池中發現之效益，包括引起較長可用壽命且無導致可能在Li電池中由於Li金屬之高度反應性性質而遇到之過熱、破裂或***之快速放電之問題的高電荷密度。The remaining challenges related to the performance of rechargeable batteries, especially those related to life and cycle characteristics, have therefore attracted continuous innovation in lithium ion (called Li ion in short form) technology. Conventionally, the intercalated Li compound can be used as a forming material at the cathode paired with graphite at the anode. In contrast to other battery types, Li-ion batteries have been sought for use in portable electronic devices due to their relatively high energy density and are limited to no memory effect, such as multiple charge-discharges involving partial discharge and relatively low self-discharge. The memory effect encountered by conventional nickel-cadmium and nickel-metal hydride rechargeable batteries that lose their ability to store charge during the cycle. Therefore, Li-ion batteries provide many of the benefits found in primary Li batteries such as non-rechargeable Li batteries, including causing a longer usable life without causing overheating that may be encountered in Li batteries due to the highly reactive nature of Li metal , Rupture or exploded rapid discharge problem of high charge density.

為輔助Li離子電池容量、循環能力以及電力輸送之發展，非晶碳已與Li一起被視為用以形成Li離子電池電極之形成材料。然而，該等電極持續受相對低導電性及高電荷轉移阻力影響，此舉導致高極化或內部電力損失。在產生其他潛在問題之中，習知以非晶碳為主之陽極材料傾向於產生高不可逆容量。In order to assist the development of Li-ion battery capacity, cycle capacity, and power transmission, amorphous carbon has been used together with Li as a forming material for forming Li-ion battery electrodes. However, these electrodes continue to be affected by relatively low conductivity and high charge transfer resistance, which results in high polarization or internal power loss. Among other potential problems, conventional anode materials mainly made of amorphous carbon tend to produce high irreversible capacity.

發明概要Summary of the invention

提供此發明內容以按簡化形式引入下文在實施方式中進一步描述之精選概念。此發明內容不意欲識別所主張主題之關鍵特點或基本特點，其亦不意欲限制所主張主題之範疇。This content of the invention is provided to introduce in a simplified form the selected concepts that are further described in the embodiments below. This summary does not intend to identify the key features or basic characteristics of the claimed subject matter, nor does it intend to limit the scope of the claimed subject matter.

本揭露內容中所描述之主題之一個創新態樣可以鋰(Li)離子電池之形式實施，該Li離子電池包括陽極、與陽極相對定位之陰極、定位於陽極與陰極之間之多孔隔板以及與陽極及陰極接觸之液體電解質。陽極包括導電基體。第一膜沈積於導電基體上。第一膜包括第一濃度之經組配以界定第一膜之第一導電性的彼此接觸之碳粒子。碳粒子中之各者包括由少層石墨烯片形成之多個聚集體。形成多孔結構之多個聚集體經組配以經歷鋰化。An innovative aspect of the subject described in this disclosure can be implemented in the form of a lithium (Li) ion battery including an anode, a cathode positioned opposite to the anode, a porous separator positioned between the anode and the cathode, and Liquid electrolyte in contact with anode and cathode. The anode includes a conductive substrate. The first film is deposited on the conductive substrate. The first film includes a first concentration of carbon particles in contact with each other configured to define the first conductivity of the first film. Each of the carbon particles includes multiple aggregates formed of few-layer graphene sheets. The multiple aggregates forming the porous structure are assembled to undergo lithiation.

鋰化可包括間夾操作或鍍覆操作中之任一者或多者。陽極及陰極中之各者可包括電活性材料。多孔結構經組配以在少層石墨烯片之接觸點之間提供電傳導。多孔結構可經組配以含有熔融Li金屬。多孔結構可經組配以接納液體電解質，該液體電解質可經組配以促進多個Li離子在多孔結構內之運輸。The lithiation may include any one or more of a pinching operation or a plating operation. Each of the anode and cathode may include electroactive materials. The porous structure is configured to provide electrical conduction between the contact points of the few graphene sheets. The porous structure can be configured to contain molten Li metal. The porous structure can be configured to receive a liquid electrolyte, and the liquid electrolyte can be configured to facilitate the transportation of multiple Li ions within the porous structure.

第二膜可沈積於第一膜上。第二膜可包括第二濃度之以碳為主之粒子。第二濃度之以碳為主之粒子經組配以提供低於第一導電性之第二膜之第二導電性。電活性材料可駐存於陽極及陰極中之一者或二者之孔隙中。電活性材料之比表面積(SSA)可介於約1,635 m² /g與2,675 m² /g之間。電活性材料可包括以下中之任一者或多者：預鋰化少層石墨烯(FLG)片、初始石墨烯、氧化石墨烯、還原氧化石墨烯、氟化石墨烯、氯化石墨烯、溴化石墨烯、碘化石墨烯、氫化石墨烯、氮化石墨烯、硼摻雜石墨烯、氮摻雜石墨烯、化學官能化石墨烯、其物理或化學活化或蝕刻型式、硫摻雜石墨烯或其導電聚合物塗佈或接枝型式。The second film can be deposited on the first film. The second film may include a second concentration of carbon-based particles. The second concentration of carbon-based particles is assembled to provide a second conductivity lower than the first conductivity of the second film. The electroactive material may reside in the pores of one or both of the anode and the cathode. The specific surface area (SSA) of the electroactive material may be between about 1,635 m ² /g and 2,675 m ² /g. The electroactive material may include any one or more of the following: pre-lithiated few-layer graphene (FLG) sheets, initial graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, Brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, its physical or chemical activation or etching pattern, sulfur-doped graphene Coating or grafting type of olefin or its conductive polymer.

多孔結構可由不依賴於黏合劑之聚集體界定且經組配以成型為尺寸為介於1-30 μm範圍內、＜ 50 μm或高於500 nm中之任一者或多者之實質上球形形狀。多孔結構可包括經組配以併有矽(Si)之活性Li間夾結構。活性Li間夾結構之比容量可介於約730 - 3,600 mAh/g之間。化學官能化石墨烯可包括選自以下之官能基：醌、氫醌、四級銨化芳胺、硫醇、二硫化物、磺酸酯(- SO₃ )、過渡金屬氧化物、過渡金屬硫化物或其組合，以上物質包括經組配以與以下中之任一者或多者反應或併有以下中之任一者或多者之官能基：鎂(Mg)、鈣(Ca)、鋁(Al)、鍶(Sn)以及鋅(Zn)。The porous structure can be defined by aggregates that do not rely on binders and are assembled to be shaped into a substantially spherical shape with a size in the range of 1-30 μm, <50 μm or more than 500 nm. shape. The porous structure may include an active Li sandwich structure combined with silicon (Si). The specific capacity of the active Li sandwich structure can be between about 730-3,600 mAh/g. Chemically functionalized graphene may include functional groups selected from the group consisting of: quinone, hydroquinone, quaternary ammonium arylamine, mercaptan, disulfide, sulfonate (-SO ₃ ), transition metal oxide, transition metal sulfide The above substances include functional groups that are formulated to react with any one or more of the following or have any one or more of the following: magnesium (Mg), calcium (Ca), aluminum (Al), Strontium (Sn), and Zinc (Zn).

導電基體可為集電器，該集電器可至少部分以發泡體為主或衍生於發泡體且選自以下中之任一者或多者：金屬發泡體、金屬網、金屬篩網、穿孔金屬、以片材為主之3D結構、金屬纖維墊、金屬奈米線墊、導電聚合物奈米纖維墊、導電聚合物發泡體、導電聚合物塗佈的纖維發泡體、碳發泡體、石墨發泡體、碳氣凝膠、碳乾凝膠、石墨烯發泡體、氧化石墨烯發泡體、還原氧化石墨烯發泡體、碳纖維發泡體、石墨纖維發泡體以及剝離型石墨發泡體。The conductive matrix may be a current collector, which may be at least partially foam-based or derived from foam and selected from any one or more of the following: metal foam, metal mesh, metal mesh, Perforated metal, sheet-based 3D structure, metal fiber mat, metal nanowire mat, conductive polymer nanofiber mat, conductive polymer foam, conductive polymer coated fiber foam, carbon hair Foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, and Exfoliated graphite foam.

集電器可成型為箔。電活性材料可包括以下中之一或多者：無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片。無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片可選自硒化鉍或碲化鉍、過渡金屬二硫屬化物或三硫屬化物、過渡金屬硫化物、硒化物或碲化物、氮化硼或其組合，其中奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片之厚度小於100 nm。The current collector can be shaped as a foil. The electroactive material may include one or more of the following: inorganic materials, nano particles, nano disks, nano flakes, nano coatings or nano flakes. Nanoparticles, nanoplates, nanosheets, nano coatings or nanosheets of inorganic materials can be selected from bismuth selenide or bismuth telluride, transition metal dichalcogenides or trichalcogenides, transition metal sulfides, Selenide or telluride, boron nitride or a combination thereof, wherein the thickness of the nanoparticle, nanodisk, nanosheet, nano coating or nanosheet is less than 100 nm.

本揭露內容中所描述之主題之另一創新態樣可以電化電池電極之形式實施，該電化電池電極包括沈積於導電基體上之膜層。膜層包括一定濃度之由正交熔合在一起之多個少層石墨烯片形成之碳聚集體及由多個少層石墨烯片界定之多孔結構。多孔結構經組配以進行以下中之任一者或多者：在多個少層石墨烯片中之任二個或更多個之間之接觸點之間提供電傳導或容納電活性材料。Another innovative aspect of the subject described in this disclosure can be implemented in the form of an electrochemical cell electrode, which includes a film layer deposited on a conductive substrate. The film layer includes a certain concentration of carbon aggregates formed by orthogonally fused together a plurality of few-layer graphene sheets and a porous structure defined by a plurality of few-layer graphene sheets. The porous structure is configured to perform any one or more of the following: provide electrical conduction or contain electroactive materials between the contact points between any two or more of the plurality of few-layer graphene sheets.

多個少層石墨烯片之一或多對鄰接石墨烯片可包括藉由3Å至20Å之D-間距間隔開之第一石墨烯片及第二石墨烯片。電化電池電極可包含陽極，其中電活性材料包括散佈於陽極中之D-間距中之元素鋰(Li)。多個Li離子由元素Li提供。One or more pairs of adjacent graphene sheets of the plurality of few-layer graphene sheets may include a first graphene sheet and a second graphene sheet separated by a D-spacing of 3 Å to 20 Å. The electrode of an electrochemical cell may include an anode, wherein the electroactive material includes the element lithium (Li) dispersed in the D-spacing in the anode. Multiple Li ions are provided by the element Li.

額外膜沈積於該膜上。該膜經組配以提供第一導電性且額外膜經組配以提供不同於第一導電性之第二導電性。An additional film is deposited on the film. The film is configured to provide a first conductivity and the additional film is configured to provide a second conductivity different from the first conductivity.

多孔結構可包括經組配以被液相電解質浸潤之多個互連通道。第一導電性及第二導電性均可與液相電解質中由電活性材料提供之多個Li離子之遷移成正比。遷移可朝向與電化電池電極實質上相對定位之額外電化電池電極。多個互連通道可經組配以防止電化電池電極或額外電化電池電極中之任一者或多者上之Li離子積聚。The porous structure may include a plurality of interconnected channels configured to be infiltrated by the liquid electrolyte. Both the first conductivity and the second conductivity are proportional to the migration of multiple Li ions provided by the electroactive material in the liquid electrolyte. Migration may be towards additional electrochemical cell electrodes positioned substantially opposite to the electrochemical cell electrodes. Multiple interconnecting channels can be configured to prevent the accumulation of Li ions on any one or more of the electrode of the electrochemical cell or the electrode of the additional electrochemical cell.

多孔結構可包括中尺度建構或微米尺度碎形建構中之任一者或多者。電活性材料可包括可經組配以被灌注至多孔結構中之熔融Li金屬。The porous structure may include any one or more of a mesoscale structure or a microscale fractal structure. The electroactive material can include molten Li metal that can be configured to be poured into the porous structure.

多孔結構可經組配以被電解質浸潤，該電解質可經組配以運輸Li離子。多孔結構可經組配以被於液相或凝膠相中之任一者或多者中之電解質浸潤。電解質可處於聚合物相或實質上固體電解質中間相中之任一者或多者中，該實質上固體電解質中間相可包括固態電解質，該固態電解質可經組配以至少實質上防止或減少Li樹枝狀結晶形成、短路形成或固態電解質滲漏中之任一者或多者。The porous structure can be configured to be infiltrated by an electrolyte, and the electrolyte can be configured to transport Li ions. The porous structure may be configured to be infiltrated by the electrolyte in any one or more of the liquid phase or the gel phase. The electrolyte may be in any one or more of a polymer phase or a substantially solid electrolyte intermediate phase. The substantially solid electrolyte intermediate phase may include a solid electrolyte, which may be configured to at least substantially prevent or reduce Li Any one or more of dendritic crystal formation, short circuit formation, or solid electrolyte leakage.

固態電解質可選自固體聚合物電解質、凝膠聚合物電解質或非聚合物電解質中之任一者或多者。固態電解質可包括溶解於聚合物主體中之Li鹽，該聚合物主體可包括以下中之任一者或多者：聚乙二醇(PEO)、聚偏二氟乙烯(polyvinylidene fluoride/polyvinylidene difluoride，PVDF)、聚(對苯醚) (PPO)或聚、聚(偏二氟乙烯-共-六氟丙烯) (PVDF-HFP)、聚(甲基丙烯酸甲酯) (PMMA)、聚苯乙烯磺酸酯(PSS)以及此等聚合物之鹽(Li或Na鹽)、PAN、PANI。The solid electrolyte may be selected from any one or more of solid polymer electrolytes, gel polymer electrolytes, and non-polymer electrolytes. The solid electrolyte may include Li salt dissolved in a polymer body, and the polymer body may include any one or more of the following: polyethylene glycol (PEO), polyvinylidene fluoride/polyvinylidene difluoride, PVDF), poly(p-phenylene oxide) (PPO) or poly, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(methyl methacrylate) (PMMA), polystyrene sulfonate Acid ester (PSS) and the salt of these polymers (Li or Na salt), PAN, PANI.

實質上固體電解質中間相可包括於聚合物基質中捕集之液體組分或非聚合物固體電解質中之一者或另一者。液體組分經組配以促進Li離子運輸。非聚合物固體電解質可包括以下中之任一者或多者：實質上陶瓷材料或Li超離子導體(LISICON)、包括石榴石型Li₇ La₃ Zr₂ O₁₂ (LLZO)之併有陶瓷奈米纖維之複合材料、包括鈣鈦礦由鈦酸鈣構成之氧化鈣鈦礦物。非聚合物固體電解質之厚度可介於約0.5 μm至40 μm範圍內。厚度可經組配以實質上防止Li樹枝狀結晶形成或生長中之任一者或多者。The substantially solid electrolyte intermediate phase may include one or the other of a liquid component trapped in a polymer matrix or a non-polymer solid electrolyte. The liquid components are formulated to promote Li ion transport. The non-polymer solid electrolyte may include any one or more of the following: essentially ceramic materials or Li super ionic conductors (LISICON), including garnet-type Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) and ceramics The composite material of rice fiber, including perovskite is perovskite mineral composed of calcium titanate. The thickness of the non-polymer solid electrolyte may range from about 0.5 μm to 40 μm. The thickness can be configured to substantially prevent any one or more of the formation or growth of Li dendrites.

多孔結構中之通道可包括經組配以提供Li離子管道之第一部分、經組配以促進快速Li離子運輸之第二部分以及經組配以限制電活性材料之第三部分。導電性介於約1,000 S/m與約20,000 S/m之間之範圍內。The channels in the porous structure may include a first part configured to provide Li ion channels, a second part configured to promote rapid Li ion transport, and a third part configured to confine the electroactive material. The conductivity is in the range between about 1,000 S/m and about 20,000 S/m.

一或多個額外膜層可沈積於該膜層上，該一或多個額外膜層中之任一個或多個經組配以提供相對於緊接在前之膜層而言在與導電基體實質上正交之方向成比例地降低之導電性。One or more additional film layers may be deposited on the film layer, and any one or more of the one or more additional film layers are configured to provide a conductive substrate with respect to the immediately preceding film layer. The substantially orthogonal directions decrease the conductivity proportionally.

固體-電解質界面(SEI)可形成於多孔結構之鄰近區域內。電化電池可進一步包含定位於多孔結構之鄰近區域內之人工固體-電解質界面(ASEI)。ASEI在多孔結構形成期間原位形成或異地形成為塗層、膜或反應物中之任一者或多者。The solid-electrolyte interface (SEI) can be formed in the vicinity of the porous structure. The electrochemical cell may further include an artificial solid-electrolyte interface (ASEI) positioned in the vicinity of the porous structure. ASEI is formed in situ or heterogeneously formed as any one or more of coatings, membranes, or reactants during the formation of the porous structure.

多孔結構可包括可經組配以提供Li吸附中心之一或多個親鋰官能化表面。The porous structure can include one or more lithium-philic functionalized surfaces that can be configured to provide Li adsorption centers.

本揭露內容中所描述之主題之一個創新態樣可以製造陽極之方法之形式實施。該方法可包括以第一濃度位準成核多個碳粒子，基於第一濃度位準在犧牲基體上形成第一膜，碳粒子中之各者利用由熔合在一起之少層石墨烯片形成之多個聚集體界定，基於少層石墨烯片界定多孔結構，及將熔融鋰(Li)金屬灌注至多孔結構中。An innovative aspect of the subject described in this disclosure can be implemented in the form of a method of manufacturing anodes. The method may include nucleating a plurality of carbon particles at a first concentration level, forming a first film on the sacrificial substrate based on the first concentration level, and each of the carbon particles is formed by using a few layers of graphene sheets fused together The multiple aggregates are defined, based on a few graphene sheets to define a porous structure, and molten lithium (Li) metal is poured into the porous structure.

多個互連多孔通道可基於多個碳粒子來加以界定。第二膜可藉由在第一膜上以第二濃度位準成核碳粒子來形成。第一膜可經組配以提供第一導電性且第二膜可經組配以提供不同於第一導電性之第二導電性。第二導電性可低於第一導電性。The plurality of interconnected porous channels may be defined based on the plurality of carbon particles. The second film can be formed by nucleating carbon particles at a second concentration level on the first film. The first film may be configured to provide a first conductivity and the second film may be configured to provide a second conductivity different from the first conductivity. The second conductivity may be lower than the first conductivity.

第一膜之平均厚度可介於約10 µm與約200 µm之間之範圍內。碳粒子可在卷軸式處理設備上生長。該方法可包括以下中之任一者或多者：將熔融Li金屬氣化至金屬箔上以及將熔融Li金屬自金屬箔捲至多孔結構中。該方法可包括以下中之任一者或多者：製備陽極以與藉由化學官能化或硫化中之任一者或多者製備之陰極一起參與Li離子之可逆遷移以及在多孔結構上使多個石墨烯薄片緻密。The average thickness of the first film may be in the range between about 10 µm and about 200 µm. Carbon particles can be grown on reel-type processing equipment. The method may include any one or more of the following: vaporizing molten Li metal onto the metal foil and rolling the molten Li metal from the metal foil into the porous structure. The method may include any one or more of the following: preparing an anode to participate in the reversible migration of Li ions together with a cathode prepared by any one or more of chemical functionalization or sulfidation, and making a more porous structure. The graphene flakes are dense.

本揭露內容中所描述之主題之另一態樣可以用於產生鋰(Li)離子電池陽極之方法之形式實施。該方法可包括在基體上沈積第一多個碳粒子以及形成經組配以基於第一多個碳粒子提供第一導電性之第一膜。第一多個碳粒子中之各碳粒子可包括由正交熔合在一起之少層石墨烯片形成且經組配以界定多孔結構之多個3D聚集體。多孔配置形成於多孔結構中。將熔融Li金屬灌注至多孔結構中。該方法可包括以下中之任一者或多者：在第一膜上沈積第二多個碳粒子以及形成經組配以基於第二多個碳粒子提供第一導電性之第二膜。Another aspect of the subject matter described in this disclosure can be implemented in the form of a method for producing lithium (Li) ion battery anodes. The method may include depositing a first plurality of carbon particles on a substrate and forming a first film configured to provide a first conductivity based on the first plurality of carbon particles. Each of the carbon particles in the first plurality of carbon particles may include a plurality of 3D aggregates formed of a few graphene sheets orthogonally fused together and assembled to define a porous structure. The porous configuration is formed in the porous structure. The molten Li metal is poured into the porous structure. The method may include any one or more of the following: depositing a second plurality of carbon particles on the first film and forming a second film configured to provide a first conductivity based on the second plurality of carbon particles.

熔融Li金屬之灌注速率可基於熔融Li金屬之黏性阻力來進行選擇。熔融Li金屬可經組配以與第一多個碳粒子中之任一個或多個反應來產生碳化物。該方法可包括以下中之任一者或多者：將於氣相中之熔融Li金屬浸潤至多孔結構中，在由熔融Li金屬提供之任一個或多個Li離子與多孔結構之一或多個暴露表面之間引發化學反應，以及由一或多個暴露表面形成一或多個親鋰表面。The infusion rate of the molten Li metal can be selected based on the viscosity resistance of the molten Li metal. The molten Li metal can be configured to react with any one or more of the first plurality of carbon particles to produce carbides. The method may include any one or more of the following: infiltrating the molten Li metal in the gas phase into the porous structure, and one or more of any one or more Li ions provided by the molten Li metal and the porous structure. A chemical reaction is initiated between the two exposed surfaces, and one or more lithium-philic surfaces are formed from the one or more exposed surfaces.

該方法可包括用包括鹵素或金屬氧化物中之任一者或多者之活性元素塗佈親鋰表面中之任一個或多個。該方法可包括用具有低於Li之表面能之任一個或多個元素塗佈親鋰表面中之任一個或多個以及用具有低於Li之表面能之任一個或多個元素促進親鋰表面中之任一個或多個之Li潤濕增強。The method may include coating any one or more of the lithium-philic surfaces with active elements including any one or more of halogens or metal oxides. The method may include coating any one or more of the lithium-philic surface with any one or more elements having a surface energy lower than Li and promoting the lithium-philic surface with any one or more elements having a surface energy lower than Li Li wetting of any one or more of the surfaces is enhanced.

該方法可包括藉由將金屬粉末或包括碳化矽(SiC)之含金屬化合物中之任一者或多者併入碳預形成物中來產生黏合劑。Li潤濕可包括對界面表面張力進行工程改造。在一些態樣中，Li潤濕包含Li界面及多孔結構之暴露表面處之一或多個化學反應。Li潤濕增強可包括以下中之任一者或多者：在界面處添加一定量之摻雜劑以及影響對應於該量摻雜劑之Li潤濕之程度。The method may include generating a binder by incorporating any one or more of metal powder or a metal-containing compound including silicon carbide (SiC) into a carbon preform. Li wetting can include engineering the interfacial surface tension. In some aspects, Li wetting includes one or more chemical reactions at the Li interface and the exposed surface of the porous structure. Li wetting enhancement may include any one or more of the following: adding a certain amount of dopant at the interface and affecting the degree of Li wetting corresponding to the amount of dopant.

較佳實施例之詳細說明Detailed description of the preferred embodiment

新穎系統、設備以及方法之各種態樣係參照隨附圖式更完整地描述於本文中。然而，所揭露之教示內容可以許多不同形式來體現，且不應被解釋為限於貫穿本揭露內容所呈現之任何特定結構或功能。相反地，此等態樣經提供以使得本揭露內容透徹且完整，且向熟習此項技術者充分傳達本揭露內容之範疇。Various aspects of the novel system, equipment, and method are described more fully in this article with reference to the accompanying drawings. However, the disclosed teaching content can be embodied in many different forms, and should not be construed as being limited to any specific structure or function presented throughout the present disclosure. On the contrary, these aspects are provided to make the contents of the disclosure thorough and complete, and to fully convey the scope of the contents of the disclosure to those familiar with the technology.

基於本文中之教示內容，熟習此項技術者應瞭解本揭露內容之範疇意欲涵蓋不論是否不依賴於本發明之任何其他態樣或與之組合而實施的本文所揭露之新穎系統、設備以及方法的任何態樣。舉例而言，設備可使用任何數目之本文所闡述之態樣來實施，或方法可使用任何數目之本文所闡述之態樣來實踐。另外，本發明之範疇意欲涵蓋使用除本文所闡述之本發明之各種態樣之外或不同於本文所闡述之本發明之各種態樣的其他結構、功能或結構與功能來實踐的此類設備或方法。本文所揭露之任一態樣可由申請專利範圍之一或多個元素來體現。Based on the teachings in this article, those familiar with the technology should understand that the scope of the disclosure is intended to cover the novel systems, devices, and methods disclosed in this article that are implemented regardless of whether or not relying on any other aspects of the present invention or in combination with them. Any aspect of. For example, the device can be implemented using any number of aspects described herein, or the method can be practiced using any number of aspects described herein. In addition, the scope of the present invention is intended to cover such devices that are practiced using other structures, functions, or structures and functions other than the various aspects of the present invention described herein or different from the various aspects of the present invention described herein Or method. Any aspect disclosed herein can be embodied by one or more elements in the scope of the patent application.

儘管一些實例及態樣描述於本文中，但此等實例之許多變化及排列屬於本揭露內容之範疇內。儘管較佳態樣之一些效益及優點被提及，但本揭露內容之範疇不意欲限於效益、用途或目標。相反地，本揭露內容之態樣意欲廣泛地適用於在諸如甲烷之含碳氣體之大氣壓蒸氣流物料流中自成核的以碳為主之粒子、包括界定於其中之空隙空間及離子管道之石墨烯片之多個導電三維(3D)聚集體的以碳為主之粒子，其中一些例示於圖式及以下較佳態樣描述中。詳細描述及圖式僅例示本揭露內容而非限制本揭露內容，本揭露內容之範疇由所附申請專利範圍及其等效物界定。定義 Li 離子 電池 Although some examples and aspects are described herein, many variations and arrangements of these examples fall within the scope of the present disclosure. Although some benefits and advantages of the better aspect are mentioned, the scope of this disclosure is not intended to be limited to benefits, uses, or goals. On the contrary, the aspect of the present disclosure is intended to be widely applicable to the self-nucleating carbon-based particles in the atmospheric vapor stream of carbon-containing gas such as methane, including void spaces and ion channels defined therein. The graphene sheet consists of a plurality of conductive three-dimensional (3D) aggregates of carbon-based particles, some of which are exemplified in the diagram and the description of the preferred configuration below. The detailed description and drawings only illustrate the content of the disclosure and do not limit the content of the disclosure. The scope of the disclosure is defined by the scope of the attached patent application and its equivalents. Define Li- ion battery

Li離子電池為一種類型之二次電池，該二次電池可替代地被稱為可充電電池。近年來，該電池技術已顯示作為電源之巨大前景，該等電源可藉由促進EV在許多應用中之廣泛實施來引起電動車(EV)旋轉。因此，用於Li離子電池之各種組件之新型材料之研發為材料科學領域中之研究焦點。Li離子電池供電大部分現代可攜裝置且似乎已克服消費大眾較大規模使用該等高能量密度裝置以用於諸如EV之要求較高應用之心理障礙。The Li-ion battery is a type of secondary battery, which may alternatively be referred to as a rechargeable battery. In recent years, the battery technology has shown great promise as a power source that can cause electric vehicles (EV) to spin by facilitating the widespread implementation of EVs in many applications. Therefore, the research and development of new materials for various components of Li-ion batteries is the focus of research in the field of materials science. Li-ion batteries power most modern portable devices and seem to have overcome the psychological barrier of the consumer masses using these high energy density devices on a larger scale for more demanding applications such as EVs.

關於操作，在Li離子電池中，Li離子(Li+)在放電循環期間自亦稱為陽極之負電極開始遷移，通過可處於液相或凝膠相中之任一者或多者中之電解質，到達正電極且在充電循環期間返回。習知Li離子電池可使用間夾Li化合物在正電極處作為形成材料且在負電極處作為石墨。該等電池之特徵可在於作為具有毫安小時/公克(mAh/g)單位之比容量量測之其相對高能量密度、無「記憶效應」-描述其中若鎳-鎘電池在僅部分放電之後重複再充電，則其逐漸損失其最大能量容量之情形-及低自放電。令人遺憾地，與許多非Li習知電池化學性質不同，Li離子電池可由於元素及離子Li之高度反應性性質而呈現安全隱患。Li電池可能出乎意料地劣化，包括貫穿到擊穿、磨擦接觸或甚至過度充電時之***及起火。儘管有該等缺點，但高能量密度之Li離子電池仍保持具有吸引力，此係因為其准許充電循環之間數小時較長可使用壽命以及較長循環壽命，該循環壽命係指在多個重複充電-放電(諸如部分或總體充電耗乏)循環內給定Li離子電池之電流輸送或輸出效能。Regarding operation, in Li-ion batteries, Li ions (Li+) start to migrate from the negative electrode, also known as the anode, during the discharge cycle through the electrolyte that can be in either or more of the liquid phase or the gel phase, Reach the positive electrode and return during the charging cycle. The conventional Li-ion battery can use an intervening Li compound as a forming material at the positive electrode and as graphite at the negative electrode. These batteries can be characterized by their relatively high energy density as a measurement of specific capacity in milliampere-hour/gram (mAh/g) units, and no "memory effect"-described in which if the nickel-cadmium battery is only partially discharged after Repeated recharging, it gradually loses its maximum energy capacity-and low self-discharge. Unfortunately, unlike many conventional non-Li battery chemistries, Li-ion batteries can present safety hazards due to the highly reactive nature of the element and ion Li. Li batteries may deteriorate unexpectedly, including explosions and fires that penetrate through to breakdown, frictional contact, or even overcharging. Despite these shortcomings, high-energy density Li-ion batteries remain attractive because they allow a long service life of several hours between charging cycles and a long cycle life. The cycle life refers to multiple The current delivery or output performance of a given Li-ion battery within a repeated charge-discharge cycle (such as partial or total charge depletion).

總體而言，Li金屬由於相較於標準氫電極而言其高理論比容量(3,860 mAh/g)、低密度(0.59 g cm⁻³ )以及低負電化電位(諸如−3.040 V)而仍顯現為用於二次Li離子電池之負電極之理想材料。但諸如樹枝狀結晶生長之問題持續存留，該樹枝狀結晶生長係指可能由Li沈澱物造成之電池自身內分支樹狀結構之生長。樹枝狀結晶在自一個電極生長以接觸另一電極時可能會造成短路相關嚴重安全問題及受限庫倫效率(Coulombic efficiency)，該庫倫效率為對在Li離子電池中所固有之沈積及剝離操作期間使電子在電池中轉移之充電效率的論述。該等挑戰先前已阻礙Li離子電池應用。In general, Li metal still exhibits its high theoretical specific capacity (3,860 mAh/g), low density (0.59 g cm ⁻³ ), and low negative electrochemical potential (such as −3.040 V) compared to standard hydrogen electrodes. It is an ideal material for the negative electrode of secondary Li-ion batteries. However, problems such as dendritic crystal growth continue to persist, which refers to the growth of branched tree-like structures in the battery itself that may be caused by Li deposits. When dendrites grow from one electrode to contact another electrode, they may cause serious safety issues related to short circuits and limited Coulombic efficiency. A discussion of the charging efficiency of transferring electrons in the battery. These challenges have previously hindered the application of Li-ion batteries.

較早研發之Li二次電池之安全相關問題已引起當代Li離子二次電池之研發及改進。該等Li離子電池之特點通常在於用作陽極之含碳材料，該等含碳陽極材料包括： ●            石墨； ●            非晶碳；以及 ●            石墨化碳。 上文所呈現之第一類型之三含碳材料包括天然存在之石墨及合成石墨或人工石墨(諸如高定向熱解石墨HOPG)。任一形式之石墨可間夾有Li，諸如自熔融Li金屬源獲得之Li。所得石墨間夾化合物(GIC)可表示為Li_x C₆ ，其中X通常小於1。為限制或以其他方式最小化因用GIC進行之Li金屬置換所致之能量密度損失，Li_x C₆ 中之X必須最大化且電池之第一電荷中之不可逆容量損失(Q _ir )必須最小化。The safety-related issues of Li secondary batteries developed earlier have led to the development and improvement of contemporary Li-ion secondary batteries. These Li-ion batteries are usually characterized by carbon-containing materials used as anodes. Such carbon-containing anode materials include: ● graphite; ● amorphous carbon; and ● graphitized carbon. The first type three carbon-containing materials presented above include naturally occurring graphite and synthetic graphite or artificial graphite (such as highly oriented pyrolytic graphite HOPG). Any form of graphite can be interposed with Li, such as Li obtained from a molten Li metal source. The resulting graphite intercalation compound (GIC) can be expressed as Li _x C ₆ , where X is usually less than 1. In order to limit or otherwise minimize the energy density loss due to Li metal replacement with GIC _{, X in Li x} C ₆ must be maximized and the irreversible capacity loss (Q _ir ) in the first charge of the battery must be minimized change.

因此，一般咸信可被可逆地間夾至完美石墨晶體之石墨烯平面之間之間隙中之最大量Li出現在對應於理論372 mAh/g之由Li_x C₆ (x=1)表示之石墨間夾化合物中。然而，此類受限比容量不可充分地滿足現代電子設備及EV之較高能量密度電力需要之苛刻需求。因此，諸如間夾有Li之石墨之以碳為主之陽極可由於表面-電解質界面層(SEI)之存在而展現經延長循環壽命，該SEI層係在初始若干充電-放電循環期間由Li與周圍電解質之間或Li與陽極表面/邊緣原子或官能基之間之反應產生。指SEI形成之此反應中消耗之Li離子可衍生於原先意欲用於電荷轉移之Li離子中之一些，該電荷轉移係指當在以碳為主之結構中，諸如在陽極內間夾有碳時元素Li之解離過程。Therefore, it is generally believed that the maximum amount of Li that can be reversibly sandwiched between the graphene planes of a perfect graphite crystal appears in the theoretical 372 mAh/g represented by Li _x C ₆ (x=1) In the graphite intercalation compound. However, such limited specific capacity cannot fully meet the demanding demands of modern electronic equipment and the higher energy density power requirements of EVs. Therefore, carbon-based anodes such as graphite with Li interposed can exhibit extended cycle life due to the presence of the surface-electrolyte interface layer (SEI), which is composed of Li and Li during the initial charge-discharge cycles. The reaction between surrounding electrolytes or between Li and anode surface/edge atoms or functional groups occurs. It means that the Li ions consumed in this reaction of SEI formation can be derived from some of the Li ions originally intended for charge transfer. The charge transfer refers to when in a carbon-based structure, such as carbon sandwiched in the anode The dissociation process of time element Li.

如與典型Li離子電池放電循環期間電子釋放及運輸以促進電流傳導來供電負載裝置相關，電荷轉移可出現在於多孔隔板上到達陰極之電解質中Li離子移動期間。在重複Li離子電池充電-放電循環期間，SEI形成，且遷移通過電解質之Li離子中之一些變成惰性SEI層之一部分且被描述為變得「不可逆」，原因在於其可不再為用於電荷轉移之活性元素或離子。因此，需要最小化用於形成有效SEI層之Li之量。除SEI形成之外，Q _ir 亦已歸因於由電解質/溶劑共間夾及其他副反應造成之石墨剝離。For example, in relation to the release and transport of electrons during the discharge cycle of a typical Li-ion battery to facilitate current conduction to power the load device, charge transfer can occur during the movement of Li ions in the electrolyte on the porous separator to the cathode. During repeated Li-ion battery charge-discharge cycles, SEI is formed, and some of the Li ions that migrate through the electrolyte become part of the inert SEI layer and are described as becoming "irreversible" because it can no longer be used for charge transfer The active element or ion. Therefore, it is necessary to minimize the amount of Li used to form an effective SEI layer. In addition to the formation of SEI, Q _ir has also been attributed to the exfoliation of graphite caused by the electrolyte/solvent sandwich and other side reactions.

接著，非晶碳不含有或含有極少微米微晶或奈米微晶且可包括「軟碳」及「硬碳」。軟碳係指可在約2,500℃或更高之溫度下石墨化之碳材料。相比之下，硬碳係指不可在高於2,500℃之溫度下石墨化之碳材料。Next, amorphous carbon does not contain or contains very few micron crystallites or nanocrystals and may include "soft carbon" and "hard carbon". Soft carbon refers to a carbon material that can be graphitized at a temperature of about 2,500°C or higher. In contrast, hard carbon refers to carbon materials that cannot be graphitized at a temperature higher than 2,500°C.

在實踐及工業中，常用作陽極活性材料之所謂之「非晶碳」可不為純非晶形的，而實際上含有某一微量之微米或奈米微晶，各微晶定義為少數石墨烯片，該少數石墨烯片定向為藉由弱凡得瓦爾力(van der Waals force)堆疊且接合在一起之底面。石墨烯片之數目可在一個與幾百個之間變化，產生諸如通常為0.34 nm至100 nm之厚度L_e 之c-方向尺寸。此等微晶之長度或寬度(L_a )通常介於數十奈米與微米之間。在此類碳材料之中，軟碳及硬碳可藉由低溫熱解(550-1,000℃)產生且在0-2.5 V範圍內展現400-800 mAh/g之可逆比容量。所謂之經增強比容量接近700 mAh/g之「卡片屋」含碳材料已產生。In practice and industry, the so-called "amorphous carbon" often used as an anode active material may not be purely amorphous, but actually contains a small amount of micron or nanocrystals, and each crystallite is defined as a small number of graphene sheets. , The few graphene sheets are oriented as the bottom surface stacked and joined together by weak van der Waals force. The number of graphene sheets may be between a few hundred and changes, such as those typically produced dimension L _e of 0.34 nm to 100 nm thickness of the c- direction. The length or width (L _a ) of these crystallites is usually between tens of nanometers and micrometers. Among such carbon materials, soft carbon and hard carbon can be produced by low-temperature pyrolysis (550-1,000°C) and exhibit a reversible specific capacity of 400-800 mAh/g in the range of 0-2.5 V. The so-called "card house" carbonaceous material with an enhanced specific capacity close to 700 mAh/g has been produced.

研究小組已藉由碾磨石墨、焦炭或碳纖維而獲得至多700 mAh/g之經增強比容量，且已在假設以下之情況下解釋額外比容量起源：在稱為「卡片屋」材料之含有一些分散石墨烯片之無序碳中，Li離子被吸附於單一石墨烯片二側上。亦已提出，Li易於鍵結至經質子鈍化碳，產生一系列邊緣定向之Li與C-H鍵。此舉可提供一些無序碳中之Li+之額外源。其他研究表明具有石墨奈米微晶之外部石墨烯片上Li金屬單層之形成。所論述之非晶碳係藉由對環氧樹脂進行熱解來製備且可稱為聚合物碳。以聚合物碳為主之陽極材料亦被研究。The research team has obtained an enhanced specific capacity of up to 700 mAh/g by grinding graphite, coke or carbon fiber, and has explained the origin of the additional specific capacity under the assumption that the material called "card house" contains some In the disordered carbon of the dispersed graphene sheet, Li ions are adsorbed on both sides of a single graphene sheet. It has also been proposed that Li easily bonds to proton-passivated carbon, resulting in a series of edge-oriented Li and C-H bonds. This can provide some additional sources of Li+ in the disordered carbon. Other studies have shown the formation of Li metal monolayers on outer graphene sheets with graphite nanocrystals. The discussed amorphous carbon is prepared by pyrolyzing epoxy resin and can be referred to as polymer carbon. Anode materials based on polymer carbon have also been studied.

化學性質、效能、成本以及安全特徵可在Li離子電池變型中變化。手持型電子設備可使用Li聚合物電池，該等Li聚合物電池使用聚合物凝膠作為電解質且使用氧化Li鈷(LiCoO₂ )作為陰極材料。此類組配可提供相對高能量密度，但可能呈現安全風險，尤其在受損時如此。磷酸Li鐵(LiFePO₄ )、Li離子氧化錳電池(LiMn₂ O₄ 、Li₂ MnO₃ 或LMO)以及氧化Li鎳錳鈷(LiNiMnCoO₂ 或NMC)全部提供較低能量密度，但提供較長可用壽命及較低起火或***可能性。因此，該等電池廣泛地用於電動工具、醫療裝備以及其他作用。特定而言，NMC常常視為用於汽車應用。 鋰 (Li )- 硫 ( S ) 電池 Chemical properties, performance, cost, and safety features can vary among Li-ion battery variants. Hand-held electronic devices can use Li polymer batteries, which use polymer gel as an electrolyte and Li cobalt oxide (LiCoO ₂ ) as a cathode material. Such combinations can provide relatively high energy density, but may present safety risks, especially when damaged. Li iron phosphate (LiFePO ₄ ), Li ion manganese oxide battery (LiMn ₂ O ₄ , Li ₂ MnO ₃ or LMO), and Li nickel manganese cobalt oxide (LiNiMnCoO ₂ or NMC) all provide lower energy density, but provide longer availability Life expectancy and low possibility of fire or explosion. Therefore, these batteries are widely used in power tools, medical equipment, and other functions. In particular, NMC is often seen as being used in automotive applications. Lithium (Li ) -Sulfur ( S ) battery

鋰硫電池在本文中稱為Li-S電池，為一種類型之可充電電池，因其高比能而著名。相對低原子量之Li及中等原子量之S引起Li-S電池在約水密度下相對輕。Lithium-sulfur battery is referred to as Li-S battery in this article. It is a type of rechargeable battery, which is famous for its high specific energy. The relatively low atomic weight of Li and the intermediate atomic weight of S cause the Li-S battery to be relatively light at about the water density.

Li-S電池可由於因使用硫得到之其較高能量密度及經降低成本而接替鋰離子電池。Li-S電池可提供約500 Wh/kg之比能，該比能比通常介於150-250 Wh/kg範圍內之許多習知Li離子電池顯著更佳。具有至多1,500個充電及放電循環之Li-S電池已被證實。儘管呈現許多優點，但Li-S電池所面臨之關鍵為聚硫化物「穿梭」效應，該聚硫化物「穿梭」效應導致活性材料自陰極漸進地滲漏，從而導致電池總體生命週期短。且極其低導電性之硫陰極需要額外質量之傳導性試劑以利用有效質量對容量之整體貢獻。S陰極自元素S向Li₂ S之大體積擴增及所需大量電解質亦為要求關注之問題領域。Li-S batteries can replace lithium-ion batteries due to their higher energy density and reduced cost due to the use of sulfur. Li-S batteries can provide a specific energy of about 500 Wh/kg, which is significantly better than many conventional Li-ion batteries that are usually in the range of 150-250 Wh/kg. Li-S batteries with up to 1,500 charge and discharge cycles have been proven. Despite presenting many advantages, the key to Li-S batteries is the "shuttle" effect of polysulfide. The "shuttle" effect of polysulfide causes the active material to gradually leak from the cathode, resulting in a short overall battery life cycle. In addition, the extremely low conductivity sulfur cathode requires additional mass of conductivity reagent to utilize the effective mass's overall contribution to the capacity. The large-volume expansion of S cathode from element S to Li ₂ S and the need for a large amount of electrolyte are also problem areas that require attention.

Li-S電池中之化學過程包括放電期間Li自陽極表面開始之溶解及向鹼金屬聚硫化物鹽中之併入以及充電時鋰向陽極之逆向鍍覆。在陽極表面處，發生金屬鋰溶解，以及在放電期間產生電子及鋰離子且在充電期間發生電沈積。半反應表示為：

(方程式1)The chemical process in Li-S batteries includes the dissolution of Li from the surface of the anode and the incorporation of alkali metal polysulfide salt during discharge, and the reverse plating of lithium to the anode during charging. At the anode surface, dissolution of metallic lithium occurs, and electrons and lithium ions are generated during discharge and electrodeposition occurs during charging. The half reaction is expressed as:

(Equation 1)

與在Li離子電池中所觀測到之情況類似，溶解及/或電沈積反應可能會隨時間推移導致固體-電解質界面(SEI)之不穩定生長問題，生成用於Li成核及樹枝狀生長之有效位點。樹枝狀生長造成Li電池中之內部短路且導致電池自身死亡。Similar to the situation observed in Li-ion batteries, the dissolution and/or electrodeposition reaction may cause unstable growth of the solid-electrolyte interface (SEI) over time, resulting in Li nucleation and dendritic growth. Effective site. The dendritic growth causes an internal short circuit in the Li battery and causes the battery itself to die.

在Li-S電池中，能量被儲存於為陰極之硫電極(S₈ )中。在電池放電循環期間，電解質中之Li離子自陽極遷移至陰極，其中S被還原成硫化鋰(Li₂ S)。在再填充階段期間，硫被再氧化成S₈ 。出於解釋目的半反應以高抽象層次表示為：

(E ° ≈ 2.15 V對Li / Li+)    (方程式2)In Li-S batteries, energy is stored in the sulfur electrode (S ₈ ) which is the cathode. During the battery discharge cycle, Li ions in the electrolyte migrate from the anode to the cathode, where S is reduced to lithium sulfide (Li ₂ S). During the refilling phase, sulfur is reoxidized to S ₈ . For explanatory purposes, the semi-reaction is expressed at a high level of abstraction as:

(E ° ≈ 2.15 V vs. Li / Li+) (Equation 2)

實際上，S成Li₂ S之還原反應顯著地更複雜且涉及根據以下次序之在漸減鏈長下之若干聚硫化Li (Li₂ S_x ，8 ＜ x ＜ 1)的形成：

(方程式3)In fact, _{the reduction reaction of S to Li 2} S is significantly more complicated and involves the formation of several polysulfide Li (Li ₂ S _x , 8 ＜ x ＜ 1) under decreasing chain length according to the following sequence:

(Equation 3)

最終產物為Li₂ S₂ 與Li₂ S之混合物而非僅純Li₂ S，此係由於Li₂ S時之緩慢還原動力學。此種情況與其中Li離子被間夾在陽極及陰極中之習知Li離子電池形成對比。舉例而言，在Li S電池系統中，各S原子可容納二個Li離子。通常，Li離子電池可僅收納0.5-0.7個鋰離子/個主體原子。因此，Li-S允許高得多之Li儲存密度。當電池放電時，聚硫化物(PS)在陰極表面上被依序還原： S₈ → Li₂ S₈ → Li₂ S₆ → Li₂ S₄ → Li₂ S₃ (方程式4)The final product is a _{mixture of Li 2} S ₂ and Li ₂ S instead of pure Li ₂ S, which is due to the slow reduction kinetics of _{Li 2 S.} This situation is in contrast to the conventional Li-ion battery in which Li ions are sandwiched between the anode and the cathode. For example, in a Li S battery system, each S atom can hold two Li ions. Generally, Li-ion batteries can only accommodate 0.5-0.7 lithium ions per host atom. Therefore, Li-S allows a much higher Li storage density. When the battery is discharged, polysulfide (PS) is sequentially reduced on the cathode surface: S ₈ → Li ₂ S ₈ → Li ₂ S ₆ → Li ₂ S ₄ → Li ₂ S ₃ (Equation 4)

在多孔擴散隔板上，S聚合物在陰極處形成為電池電荷： Li₂ S → Li₂ S₂ → Li₂ S₃ → Li₂ S₄ → Li₂ S₆ → Li₂ S₈ → S₈ (方程式5) 此等反應可類似於鈉(Na)-S電池中之反應。On the porous diffusion separator, S polymer is formed as battery charge at the cathode: Li ₂ S → Li ₂ S ₂ → Li ₂ S ₃ → Li ₂ S ₄ → Li ₂ S ₆ → Li ₂ S ₈ → S ₈ ( Equation 5) These reactions can be similar to those in sodium (Na)-S batteries.

關於Li-S電池系統之主要挑戰包括S之低相對低傳導性、其在放電時之巨大體積變化，且找到合適陰極，諸如由本發明所揭露之以碳為主之結構中之任一者構建之陰極為Li-S電池商業化的第一步。當前，習知Li S電池使用碳/硫陰極及Li陽極。硫為天然豐富的且成本相對低，但實際上不具有在25℃下5×10^-30 S⋅cm⁻¹ 之導電性。碳塗料提供缺失導電性。碳奈米纖維在較高成本缺點時提供有效電子傳導路徑及結構完整性。The main challenges for Li-S battery systems include the low relative low conductivity of S, its huge volume change during discharge, and finding a suitable cathode, such as being constructed by any of the carbon-based structures disclosed in the present invention The cathode is the first step in the commercialization of Li-S batteries. Currently, conventional Li S batteries use carbon/sulfur cathodes and Li anodes. Sulfur is naturally abundant and relatively low-cost, but it does not actually have the conductivity of ^{5×10 -30} S⋅cm ^{−1 at 25°C.} Carbon paint provides missing conductivity. Carbon nanofibers provide effective electronic conduction paths and structural integrity at high cost disadvantages.

Li-S設計之一個問題在於，當陰極中之S吸收Li時，Li_x S組合物之體積擴增發生，且Li₂ S之所預測體積擴增幾乎為原始S之體積之80%。此種情況造成陰極上之大機械應力，該大機械應力為快速衰退之主要原因。該過程減少碳(C)、S之間之接觸且防止Li離子流動至碳表面。One problem with Li-S design is that when S in the cathode absorbs Li, the volume increase of the _{Li x S composition occurs, and the predicted volume increase of Li 2} S is almost 80% of the original S volume. This situation causes a large mechanical stress on the cathode, which is the main reason for the rapid decline. This process reduces the contact between carbon (C) and S and prevents Li ions from flowing to the carbon surface.

經鋰化S化合物之機械特性很大程度上視Li含量而定，且在漸增Li含量之情況下，經鋰化S化合物之強度提高，但此增量不與Li成線性關係。大部分Li-S電池之主要短缺中之一者係關於與電解質之不合需要反應。當S及Li₂ S在大部分電解質中相對不可溶時，許多中間物聚硫化物(PS)不為使得Li₂ S_n 向電解質中之溶解可能導致有效S之不可逆損失的中間物聚硫化物(PS)。高度反應性Li作為負電極之使用造成大部分常用其他類型之電解質之解離。已研究陽極表面中保護層之使用提高電池安全，諸如使用鐵氟龍(Teflon)塗料顯示電解質穩定性提高，LIPON、Li₃ N亦展現有前景效能。The mechanical properties of the lithiated S compound largely depend on the Li content, and when the Li content is gradually increased, the strength of the lithiated S compound increases, but this increase is not linearly related to Li. One of the major shortages of most Li-S batteries is related to undesirable reactions with electrolytes. When S and Li ₂ S are relatively insoluble in most electrolytes, many intermediates, polysulfide (PS), are not the intermediate polysulfide that makes _{the dissolution of Li 2} S _n into the electrolyte may cause irreversible loss of effective S (PS). The use of highly reactive Li as a negative electrode causes the dissociation of most commonly used other types of electrolytes. The use of a protective layer on the anode surface has been studied to improve battery safety. For example, the use of Teflon coatings has shown improved electrolyte stability, and LIPON and Li ₃ N have also shown promising performance.

「穿梭」效應已被觀測到為Li-S電池中之衰退之主要原因。Li PS Li₂ S_x (6 ≤ x ≤ 8)高度可溶於常用於Li-S電池之電解質中。其形成且自陰極滲漏，且其擴散至陽極，在該陽極中其被還原成短鏈PS，且擴散回至陰極，在該陰極中長鏈PS再次形成。此過程由於電池自放電而導致活性材料自陰極之連續滲漏、鋰腐蝕、低庫倫效率以及短電池壽命。此外，「穿梭」效應造成歸因於亦以靜止狀態發生之PS緩慢溶解之Li-S電池之特徵自放電。Li-S電池中之「穿梭」效應可藉由因數f _c (0 ＜f _c ＜ 1)定量，該因數f _c 係藉由充電電壓平線區之延伸來評估。因數fc係由以下表示式給出：

(方程式6) 其中k _s 、q _up 、[S _tot ]以及I _c 分別為動力學常數、貢獻於陽極平線區之比容量、總硫濃度以及充電電流。 以碳為主之材料之電導率 The "shuttle" effect has been observed to be the main cause of decline in Li-S batteries. Li PS Li ₂ S _x (6 ≤ x ≤ 8) is highly soluble in the electrolyte commonly used in Li-S batteries. It forms and leaks from the cathode, and it diffuses to the anode, where it is reduced to short-chain PS, and diffuses back to the cathode, where the long-chain PS is formed again. This process causes continuous leakage of active material from the cathode, lithium corrosion, low coulombic efficiency, and short battery life due to battery self-discharge. In addition, the "shuttle" effect is attributed to the characteristic self-discharge of the Li-S battery, which also occurs in a static state, where the PS slowly dissolves. The Li-S cell "shuttle" effect may be by a factor _{f c (0 <f c <} 1) quantitatively, the factor f _c by lines extending in the charging voltage level of the line region evaluated. The factor fc is given by the following expression:

(Equation 6) where k _s , q _up , [ S _tot ] and I _c are the kinetic constants, the specific capacity contributed to the anode flat area, the total sulfur concentration and the charging current, respectively. Conductivity of carbon-based materials

電子設備中諸如碳奈米管(CNT)、石墨烯、非晶碳及/或結晶石墨之高傳導率碳材料之進步允許在不需要使用印刷電路板之情況下及在不使用已識別為對人類有毒性之材料或化合物之情況下將此等材料印刷至許多類型之表面上。在上文所描述之積層製造方法中之任一種或多種期間高傳導率碳作為原料材料或其他材料之使用可促進用適用於經增強功能、電力儲存及輸送以及最佳效率之微晶格結構進行的電池製造。儘管許多所描述裝置可充當諸如電池或電容器之電源，熟習此項技術者應瞭解，諸如3D印刷之印刷技術可使用諸如碳奈米管(CNT)、石墨烯、非晶碳或結晶石墨之高傳導率碳材料以形成其他電子裝置來進行組配。The advancement of high-conductivity carbon materials such as carbon nanotubes (CNT), graphene, amorphous carbon, and/or crystalline graphite in electronic devices allows the In the case of human toxic materials or compounds, these materials are printed on many types of surfaces. The use of high-conductivity carbon as a raw material or other materials during any one or more of the above-described multilayer manufacturing methods can promote the use of micro-lattice structures suitable for enhanced functions, power storage and transmission, and optimal efficiency On-going battery manufacturing. Although many of the described devices can act as power sources such as batteries or capacitors, those familiar with the art should understand that printing techniques such as 3D printing can use high-density materials such as carbon nanotubes (CNT), graphene, amorphous carbon or crystalline graphite. Conductivity carbon materials can be assembled to form other electronic devices.

使用諸如碳奈米管(CNT)、石墨烯、非晶碳或結晶石墨之高傳導率碳材料之印刷技術可在以下裝置之製造中實施且/或以其他方式併入：天線、經調諧天線、感測器、生物感測器、能量收穫機、光電池以及其他電子裝置。 石墨烯 Printing techniques using high-conductivity carbon materials such as carbon nanotubes (CNT), graphene, amorphous carbon or crystalline graphite can be implemented in the manufacture of the following devices and/or incorporated in other ways: antennas, tuned antennas , Sensors, biological sensors, energy harvesters, photovoltaic cells and other electronic devices. Graphene

石墨烯為在其中一個原子形成各頂點之二維六方晶格中呈原子單層形式之碳之同素異形體。其為包括石墨、木炭、碳奈米管以及富勒烯(fullerene)之其他同素異形體之基礎結構元素。其亦可視為無限大芳族分子，亦即平多環芳烴家族之終極案例。Graphene is an allotrope of carbon in the form of a monolayer of atoms in a two-dimensional hexagonal lattice in which one atom forms each vertex. It is the basic structural element including graphite, charcoal, carbon nanotubes and other allotropes of fullerene. It can also be regarded as an infinitely large aromatic molecule, that is, the ultimate case of a family of polycyclic aromatic hydrocarbons.

石墨烯具有將其與其他元素區分開之特殊特性集合。與其厚度成比例，其比最強鋼強約100倍。但其密度大大低於任何其他鋼，其中曲面(surfacic)質量，諸如表面相關質量為0.763毫克/平方公尺。其極有效地傳導熱及電且幾乎透明。石墨烯亦顯示甚至高於石墨之大且非線性反磁性且可藉由Nd-Fe-B磁鐵懸浮。研究人員已識別雙極電晶體效應、電荷衝擊運輸以及材料中之大量子振盪。其最終用途應用領域為廣泛的，在高級材料及複合材料中發現獨特實施，以及用作形成材料以構建可用於Li離子電池電極中之裝飾支架來增強離子運輸及電流傳導，從而產生在其他方面習知電池技術不可達到之比容量及電力輸送圖。 石墨烯化學官能化 Graphene has a special set of properties that distinguish it from other elements. In proportion to its thickness, it is about 100 times stronger than the strongest steel. But its density is much lower than any other steel, in which the surface (surfacic) mass, such as the surface-related mass, is 0.763 mg/m². It conducts heat and electricity very efficiently and is almost transparent. Graphene also shows even larger than graphite and non-linear diamagnetism and can be suspended by Nd-Fe-B magnets. Researchers have identified bipolar transistor effects, charge shock transport, and large quantum oscillations in materials. Its end-use applications are extensive. It has unique implementations found in advanced materials and composite materials, and is used as a forming material to construct decorative scaffolds that can be used in Li-ion battery electrodes to enhance ion transport and current conduction, resulting in other aspects Specific capacity and power transmission diagrams that are unattainable by conventional battery technology. Graphene chemical functionalization

官能化意指藉由更改材料表面化學物質來向材料或物質中添加新型功能、特點、能力或特性之過程。官能化用於整個化學反應、材料科學、生物工程改造、紡織品工程改造以及奈米技術中，且可藉由用化學鍵或經由吸附將分子或奈米粒子連接至材料表面、將來自氣體、液體或經溶解固體之原子、離子或分子黏著至表面以在吸附劑表面上產生吸附物膜且不對其形成共價鍵或離子鍵來執行。Functionalization refers to the process of adding new functions, features, capabilities, or characteristics to materials or substances by changing the chemical substances on the surface of the material. Functionalization is used in the entire chemical reaction, material science, bioengineering, textile engineering, and nanotechnology. It can be used to connect molecules or nanoparticles to the surface of the material by chemical bonds or through adsorption, and the The atoms, ions, or molecules of the dissolved solid are adhered to the surface to produce an adsorbate film on the surface of the adsorbent without forming a covalent bond or an ionic bond.

石墨烯片之官能化及分散可對其相應最終用途應用具有關鍵重要性。石墨烯之化學官能化使得材料能夠被諸如逐層裝配、旋塗以及過濾之溶劑輔助技術處理且亦防止單層石墨烯(SLG)在還原期間黏聚且維持石墨烯固有特性。The functionalization and dispersion of graphene sheets can be of critical importance for their corresponding end-use applications. The chemical functionalization of graphene enables the material to be processed by solvent-assisted techniques such as layer-by-layer assembly, spin coating, and filtration, and also prevents single-layer graphene (SLG) from agglomerating during reduction and maintains the inherent properties of graphene.

當前，石墨烯官能化可藉由共價及非共價改質技術來執行。在二種情況下，已進行氧化石墨烯之表面改質、接著為還原以獲得官能化石墨烯。已發現，共價及非共價改質技術均極有效地製備可處理石墨烯。Currently, graphene functionalization can be performed by covalent and non-covalent modification techniques. In both cases, surface modification of graphene oxide has been performed, followed by reduction to obtain functionalized graphene. It has been found that both covalent and non-covalent modification technologies are extremely effective in preparing processable graphene.

然而，已觀測到官能化石墨烯之導電性相較於純石墨烯而言顯著地降低。此外，藉由共價及非共價技術製備之官能化石墨烯之表面積由於片狀石墨之破壞性化學氧化、接著為音波處理、官能化以及化學還原而顯著地減小。為克服此等問題，研究已報導在一步法中直接由石墨進行之官能化石墨烯製備。在全部此等情況下，石墨烯之表面改質可防止黏聚且促進穩定分散液形成。經表面改質之石墨烯可用於製造聚合物奈米複合材料、Li離子電池電極、超電容器裝置、藥物輸送系統、太陽電池、記憶體裝置、電晶體裝置、生物感測器等。 石墨 However, it has been observed that the electrical conductivity of functionalized graphene is significantly reduced compared to pure graphene. In addition, the surface area of functionalized graphene prepared by covalent and non-covalent techniques is significantly reduced due to the destructive chemical oxidation of flake graphite, followed by sonication, functionalization, and chemical reduction. To overcome these problems, studies have reported the preparation of functionalized graphene directly from graphite in a one-step process. In all these cases, the surface modification of graphene can prevent cohesion and promote the formation of a stable dispersion. The surface-modified graphene can be used to manufacture polymer nanocomposites, Li-ion battery electrodes, supercapacitor devices, drug delivery systems, solar cells, memory devices, transistor devices, biosensors, etc. graphite

如通常所理解且如本文中所提及，石墨意指具有以六方結構排列之原子之元素碳之結晶形式。石墨係以此形式天然存在且為處於諸如大氣條件之標準條件下之碳之最穩定形式。此外，在高壓及高溫下，石墨轉化成金剛石。石墨用於鉛筆及潤滑劑中。其高傳導性使其可用於諸如電極、電池及太陽電池板之電子產品中。 卷軸式 ( R2R ) 處理 As generally understood and as mentioned herein, graphite means a crystalline form of elemental carbon with atoms arranged in a hexagonal structure. Graphite is naturally occurring in this form and is the most stable form of carbon under standard conditions such as atmospheric conditions. In addition, under high pressure and high temperature, graphite is transformed into diamond. Graphite is used in pencils and lubricants. Its high conductivity allows it to be used in electronic products such as electrodes, batteries and solar panels. Reel ( R2R ) processing

R2R處理係指在一卷可撓性塑膠或金屬箔上產生電子裝置之方法。R2R處理亦可指塗覆塗料、印刷或執行以一卷可撓性材料為起始物之其他過程以及在該等過程之後再捲繞以產生輸出卷之任何方法。此等方法及諸如壓片之其他方法可根據通用術語「轉化」分組在一起。當材料卷已被塗佈、層壓或印刷時，其隨後可在切條複捲機上切割且/或切縫成其成品尺寸。R2R processing refers to the method of producing electronic devices on a roll of flexible plastic or metal foil. R2R processing can also refer to any method of applying paint, printing, or performing other processes starting with a roll of flexible material, and winding after these processes to produce an output roll. These methods and other methods such as tableting can be grouped together under the general term "transformation." When the roll of material has been coated, laminated or printed, it can then be cut on a slitter rewinder and/or slit into its finished size.

大面積電子裝置之R2R處理可降低製造成本。利用諸如嵌入至套中之電子設備、3D印刷Li離子電池、大面積可撓性顯示器以及捲起可攜顯示器之基體之可撓性性質的其他應用可出現。 氧化還原 ( Oxidation - Reduction / Redox ) 反應 R2R processing of large-area electronic devices can reduce manufacturing costs. Other applications that take advantage of the flexible properties of electronic devices embedded in sleeves, 3D printed Li-ion batteries, large-area flexible displays, and roll-up of the matrix of the portable display may emerge. Redox (Oxidation - Reduction / Redox) Reaction

氧化還原為其中原子氧化態已改變之一種類型之化學反應。氧化還原反應之特徵在於化學物種之間之電子轉移，最常伴隨為還原劑之一個物種藉由損失電子經歷氧化，而諸如氧化劑之另一物種藉由增加電子經歷還原。據稱剝離電子之化學物種已被氧化，而據稱添加有電子之化學物種已被還原。 間夾 Redox is a type of chemical reaction in which the oxidation state of atoms has changed. Redox reactions are characterized by electron transfer between chemical species. One species most often accompanied by a reducing agent undergoes oxidation by losing electrons, while another species such as an oxidizing agent undergoes reduction by increasing electrons. The chemical species that stripped electrons were said to have been oxidized, and the chemical species that added electrons were said to be reduced. In-between

間夾意指分子或離子向具有分層結構之材料中之可逆包括或***。實例係在石墨、石墨烯以及過渡金屬二硫屬化物中發現。 Li 間夾至雙層或多層石墨烯中 Intermediation refers to the reversible inclusion or insertion of molecules or ions into a material having a layered structure. Examples are found in graphite, graphene, and transition metal dichalcogenides. Li is sandwiched between two-layer or multi-layer graphene

石墨烯之電儲存容量及石墨中之Li儲存方法當前呈現需要Li離子電池領域中之進一步發展之挑戰。因此，已作出以下努力：進一步研發具有少缺陷及主要伯納爾堆疊(Bernal stacking)組配之三維雙層石墨烯發泡體，亦即一種類型之雙層石墨烯，其中一半原子直接處於下部石墨烯片中之六角形中心內且一半原子處於一原子內；及研究其Li儲存容量、方法、動力學以及阻力。Li原子可僅儲存於石墨烯中間層中。此外，分段Li雙層石墨烯產品之各種生理化學表徵進一步顯露規則Li間夾現象且例示此二種尺寸之Li儲存模式。 電化電容器 ( EC ) The electrical storage capacity of graphene and the Li storage method in graphite are currently presenting challenges that require further development in the field of Li-ion batteries. Therefore, the following efforts have been made: to further develop a three-dimensional double-layer graphene foam with fewer defects and a main Bernal stacking composition, that is, a type of double-layer graphene, in which half of the atoms are directly at the bottom The graphene sheet is in the hexagonal center and half of the atoms are in one atom; and study its Li storage capacity, method, kinetics and resistance. Li atoms can only be stored in the middle layer of graphene. In addition, various physiochemical characterizations of segmented Li bilayer graphene products further reveal the phenomenon of regular Li intercalation and exemplify the Li storage modes of these two sizes. Electrochemical capacitor ( EC )

電化電容器(EC)亦稱為超電容器(ultracapacitor/supercapacitor)，被考慮用於混合或完全EV中。EC可補充或在特定用途中置換用於EV中以提供短暫油門突然加大(burst of power) (諸如向前推進所需、快速加速常常所需之油門突然加大)之傳統電池，包括高效能Li離子電池。傳統電池仍可用於為在正常高速公路速度下之穩速行駛提供均一電力，但具有比電池快得多釋放能量之能力之超電容器可在特定時間，諸如在如此裝備之汽車需要加速時激活且補充電池提供之電力以用於諸如匯合、通行、緊急操縱以及爬山。Electrochemical capacitors (EC), also known as ultracapacitors/supercapacitors, are considered for use in hybrid or complete EVs. EC can supplement or replace traditional batteries used in EVs in specific applications to provide a short burst of power (such as the sudden increase of the throttle required for forward advancement and rapid acceleration), including high efficiency Can Li-ion battery. Conventional batteries can still be used to provide uniform power for steady-speed driving at normal highway speeds, but ultracapacitors with the ability to release energy much faster than batteries can be activated at specific times, such as when a car so equipped needs to accelerate and Supplement the power provided by the battery for things such as meeting, passing, emergency maneuvering and climbing.

EC亦必須儲存足夠能量以提供諸如220-325哩或更長距離之可接受行駛範圍。且為相對於額外電池容量而言成為成本及重量有效的，EC必須組合充分比能及比功率與長循環壽命且亦滿足成本目標。具體而言，用於EV中之應用之EC必須儲存約400 Wh能量，能夠輸送約40 kW電力約10秒且提供諸如＞ 100,000個循環之長循環壽命。The EC must also store enough energy to provide an acceptable driving range such as 220-325 miles or more. And to be cost- and weight-effective relative to additional battery capacity, EC must combine sufficient specific energy and specific power with long cycle life and also meet cost targets. Specifically, the EC used for the application in the EV must store about 400 Wh of energy, be able to deliver about 40 kW of electricity for about 10 seconds, and provide a long cycle life such as> 100,000 cycles.

諸如大於習知電容器10至100倍之高體積電容密度之EC衍生自使用可併有支架型以石墨烯為主之材料、以其為特點及/或由其構建之多孔電極以產生大有效「板面積」且衍生自在擴散雙層中儲存能量。當施加電壓時在固體-電解質界面處天然地產生之此雙層之厚度僅為約1-2 nm，因此形成極其小有效「板分離」。在一些EC中，所儲存之能量係藉由由於諸如氧化還原電荷轉移之電化現象而在固體-電解質界面處再次發生之偽電容效應來進一步擴充。雙層電容器係基於諸如活性碳之浸入電解質中之高表面積電極材料。極化雙層係在電極-電解質界面處形成，提供高電容。綜述 前言 For example, EC, which has a high volume capacitance density 10 to 100 times greater than that of conventional capacitors, is derived from the use of materials that can be combined with scaffold-type graphene-based materials, characterized by them, and/or porous electrodes constructed from them to produce large effects. Plate area" and derived from the storage of energy in the diffusion double layer. When a voltage is applied, the thickness of the double layer that is naturally generated at the solid-electrolyte interface is only about 1-2 nm, thus forming an extremely small effective "plate separation". In some ECs, the stored energy is further expanded by the pseudo-capacitance effect that reoccurs at the solid-electrolyte interface due to electrochemical phenomena such as redox charge transfer. Double layer capacitors are based on high surface area electrode materials such as activated carbon immersed in an electrolyte. The polarized double layer is formed at the electrode-electrolyte interface to provide high capacitance. Summary foreword

關於諸如石墨烯之現代以碳為主之材料之技術進步之後已增強該等材料在諸如高級二次電池之許多最終用途領域中之應用。該等電池可採用電化Li間夾或去間夾以利用碳材料及以碳為主之材料之有利特性，該等有利特性可顯著地視其相應形態、結晶度、微晶定向以及缺陷而定。舉例而言，Li離子電池之電儲存容量可藉由選擇且整合諸如各自具有其中尺寸不大於約2 µm之小碳奈米結構之石墨及石墨烯或奈米級石墨、奈米纖維、經分離單壁碳奈米管、奈米球以及奈米級非晶碳之特定同素異形體中的諸如碳之所需奈米結構化碳材料來增強。Technological advances in modern carbon-based materials such as graphene have enhanced the applications of these materials in many end-use fields such as advanced secondary batteries. These batteries can adopt electrochemical Li intercalation or deintercalation to utilize the advantageous characteristics of carbon materials and carbon-based materials. These advantageous characteristics can be significantly determined by their corresponding morphology, crystallinity, crystallite orientation and defects . For example, the electric storage capacity of Li-ion batteries can be selected and integrated, such as graphite and graphene, or nano-grade graphite, nanofibers, separated Single-walled carbon nanotubes, nanospheres, and nano-grade amorphous carbon are required to be reinforced with nanostructured carbon materials such as carbon in specific allotropes such as carbon.

用以製造用於可充電Li電池之碳及Li離子電極之已知方法包括用於形成碳電極之步驟。此類碳電極可由藉由用於達成能夠隨後間夾有Li離子之碳電極之乙烯丙烯二烯單體黏合劑彼此黏著之石墨碳粒子構成。隨後，使碳電極與經浸潤鋰(Li)金屬反應以將自其獲得之Li離子併入電極之石墨碳粒子中。電壓可被重複施加至碳電極以最初引起Li離子之間之表面反應，且被重複施加至碳且隨後引起Li離子間夾至石墨碳粒子結晶層中。在重複施加電壓之情況下，可達成間夾以視可能需要接近理論最大值且幫助電流傳導。Known methods for manufacturing carbon and Li ion electrodes for rechargeable Li batteries include steps for forming carbon electrodes. This type of carbon electrode can be composed of graphitic carbon particles adhered to each other by an ethylene propylene diene monomer binder used to achieve a carbon electrode with Li ions therebetween. Subsequently, the carbon electrode is reacted with the infiltrated lithium (Li) metal to incorporate Li ions obtained therefrom into the graphite carbon particles of the electrode. Voltage can be repeatedly applied to the carbon electrode to initially cause a surface reaction between Li ions, and be repeatedly applied to the carbon and then cause Li ions to be sandwiched between the graphite carbon particle crystalline layer. In the case of repeated application of voltage, a gap can be achieved to approach the theoretical maximum value and help current conduction if necessary.

其他剝離型以石墨為主之混合材料組合物與以下相關： ●            能夠吸收及解吸鹼金屬或鹼金屬離子，特定而言Li離子之微米或奈米尺度粒子或塗料；以及 ●            實質上互連以形成包括界定於其中之孔隙之多孔傳導性石墨網狀結構之剝離型石墨片。 粒子或塗料駐存於網狀結構孔隙中或連接至網狀結構片。剝離型石墨量介於5重量%至90重量%範圍內且粒子數目或塗料量介於95重量%至10重量%範圍內。Other exfoliated graphite-based mixed material compositions are related to the following: ● Micron or nano-scale particles or coatings that can absorb and desorb alkali metal or alkali metal ions, specifically Li ions; and ● Exfoliated graphite sheets that are substantially interconnected to form a porous conductive graphite network structure including pores defined therein. The particles or paint reside in the pores of the network structure or are connected to the network structure sheet. The amount of exfoliated graphite is in the range of 5% to 90% by weight, and the number of particles or the amount of coating is in the range of 95% to 10% by weight.

此外，高容量以矽為主之陽極活性材料與高容量富含Li之陰極活性材料之組合已顯示為有效的。對於一些以矽為主之活性材料，補充Li顯示為改進循環效能且降低不可逆容量損失。以矽為主之活性材料可形成於具有諸如熱解碳塗料或金屬塗料之導電塗料之複合材料中，且複合材料亦可形成有諸如碳奈米纖維及碳奈米粒子之其他導電碳組分。In addition, the combination of a high-capacity anode active material dominated by silicon and a high-capacity cathode active material rich in Li has been shown to be effective. For some active materials based on silicon, supplementing with Li appears to improve cycle performance and reduce irreversible capacity loss. Active materials based on silicon can be formed in composite materials with conductive coatings such as pyrolytic carbon coatings or metal coatings, and composite materials can also be formed with other conductive carbon components such as carbon nanofibers and carbon nanoparticles .

且具有有機電解質之具有鹼金屬之已知可充電電池在使含碳電極間夾有鹼金屬時經歷極少容量損失。含碳電極可包括有包括高度石墨化相及較低石墨化相之多相組合物或可包括在高於約50℃下經受Li間夾之單相高度石墨化組合物。在重複循環時，與含碳組合物一起緊密散佈之諸如碳黑之導電絲狀材料之併有將容量損失降至最低。And the known rechargeable batteries with an alkali metal with an organic electrolyte experience very little capacity loss when the alkali metal is sandwiched between carbon-containing electrodes. The carbon-containing electrode may include a multi-phase composition including a highly graphitized phase and a less graphitized phase or may include a single-phase highly graphitized composition subjected to Li intercalation at a temperature higher than about 50°C. When the cycle is repeated, the conductive filament material such as carbon black, which is closely dispersed with the carbon-containing composition, minimizes the capacity loss.

此外，已知以Li為主之陽極材料之特徵可在於包括1 m² /g或更大含碳陽極活性材料比表面積、苯乙烯-丁二烯橡膠黏合劑以及成型為1,000奈米碳纖維之纖維直徑。該等陽極材料係用於Li電池，該等Li電池具有諸如低電極阻力、高電極強度、具有極佳滲透性之電解溶液、高能量密度以及高速充電/放電之所需特徵。負電極材料含有0.05質量%至20質量%碳纖維及0.1質量%至6.0質量%苯乙烯。丁二烯橡膠形成黏合劑且可進一步含有0.3質量%至3質量%諸如羧甲基甲基纖維素之增稠劑。In addition, it is known that Li-based anode materials can be characterized by including the ^{specific surface area of the carbon-containing anode active material of 1 m 2} /g or more, styrene-butadiene rubber adhesive, and fibers formed into 1,000 nanometer carbon fibers. diameter. The anode materials are used in Li batteries, which have the required characteristics such as low electrode resistance, high electrode strength, electrolytic solution with excellent permeability, high energy density, and high-speed charging/discharging. The negative electrode material contains 0.05% to 20% by mass of carbon fiber and 0.1% to 6.0% by mass of styrene. The butadiene rubber forms a binder and may further contain 0.3% to 3% by mass of a thickening agent such as carboxymethyl methyl cellulose.

現有技術已顯示與具有已進行以下之陽極活性材料之電池相關： ●            預鋰化；以及 ●            預粉碎。 此類陽極可用包含以下之方法來製備： ●            提供陽極活性材料； ●            將所需量之Li間夾或吸收至陽極活性材料中以產生預鋰化陽極活性材料； ●            將預鋰化陽極活性材料磨碎成平均尺寸小於10 µm、較佳＜ 1 µm且最佳＜ 200 nm之細粒，該磨碎係指藉由壓碎、研磨、切割、振動或其他方法將固體材料自一個平均粒度減小至更小平均粒度；以及 ●            組合預鋰化陽極活性材料之多個細粒與傳導性添加劑及/或黏合劑材料以形成陽極。 預鋰化粒子受Li離子傳導基質或塗佈材料保護。基質材料經奈米石墨烯薄片強化。The prior art has been shown to be relevant to batteries with anode active materials that have undergone the following: ● Pre-lithiation; and ● Pre-crushing. Such anodes can be prepared by methods including the following: ● Provide anode active materials; ● Sandwich or absorb the required amount of Li into the anode active material to produce the pre-lithiated anode active material; ● Grind the pre-lithiated anode active material into fine particles with an average size of less than 10 µm, preferably less than 1 µm, and most preferably less than 200 nm. The grinding refers to crushing, grinding, cutting, vibration or other methods Reduce the solid material from an average particle size to a smaller average particle size; and ● Combine multiple fine particles of the pre-lithiated anode active material with conductive additives and/or binder materials to form the anode. The prelithiated particles are protected by Li ion conductive matrix or coating material. The matrix material is strengthened by nanographene flakes.

石墨奈米纖維亦已被揭露且包括藉由化學取代官能化、在電化電容器中用作電極之管狀富勒烯(通常稱為「巴克管(buckytube)」)、奈米管以及原纖維。以石墨奈米纖維為主之電極增強電化電容器之效能。較佳奈米纖維具有大於約200 m² /gm之表面積且實質上不含微孔隙。Graphite nanofibers have also been disclosed and include tubular fullerenes (commonly called "buckytubes"), nanotubes, and fibrils that are functionalized by chemical substitution and used as electrodes in electrochemical capacitors. Graphite nanofiber-based electrodes enhance the performance of electrochemical capacitors. Preferred nanofibers have a surface area greater than about 200 m ² /gm and are substantially free of micropores.

且已知高表面積碳奈米纖維具有於其上形成多孔高表面積層之外表面。製造高表面積碳奈米纖維之方法包括在低於聚合物塗層物質熔融溫度之溫度下熱解設置於碳奈米纖維外表面上之聚合物塗層物質。用作約高表面積碳奈米纖維之聚合物塗層物質可包括諸如甲醛、聚丙烯腈、苯乙烯、二乙烯基苯、纖維素聚合物以及環三聚二乙炔基苯之酚醛樹脂。涵蓋碳奈米纖維之高表面積聚合物可經一或多個官能基官能化。 合成本發明所揭露之碳 It is also known that high surface area carbon nanofibers have an outer surface on which a porous high surface area layer is formed. The method of manufacturing high surface area carbon nanofibers involves pyrolyzing the polymer coating material placed on the outer surface of the carbon nanofiber at a temperature lower than the melting temperature of the polymer coating material. The polymer coating materials used for high surface area carbon nanofibers may include phenolic resins such as formaldehyde, polyacrylonitrile, styrene, divinylbenzene, cellulosic polymers, and cyclotrimeric diethynylbenzene. The high surface area polymer covering carbon nanofibers can be functionalized with one or more functional groups. Synthesis of the carbon disclosed in the present invention

如上文所呈現，習知間夾有Li之以碳為主之組合物或化合物可包括諸如以下之傳統電池電極材料： ●            石墨烯或多層3D石墨烯粒子； ●            導電碳粒子；以及 ●            諸如以諸如液體之流體形式及/或以顆粒形式提供之黏合劑之黏合劑，其經組配以將以碳為主之粒子保留在其相應所需位置中且為以碳為主之系統提供總體結構完整性。As presented above, conventional carbon-based compositions or compounds with Li sandwiched can include traditional battery electrode materials such as: ● Graphene or multilayer 3D graphene particles; ● Conductive carbon particles; and ● Adhesives such as those provided in the form of fluids such as liquids and/or in the form of particles, which are configured to retain carbon-based particles in their corresponding desired positions and are carbon-based systems Provide overall structural integrity.

在習知技術中，粒子通常全部被沈積，諸如滴加至由諸如銅之金屬箔製成之現有包括漿料澆鑄電極之集電器中。漿料通常經製備以含有稱為NMP之有機黏合劑或黏合劑材料、在石化及塑膠工業中用作溶劑、採用其非揮發性及溶解多樣材料之能力之由5員內醯胺組成之有機化合物。活性材料與傳導性碳或以碳為主之粒子之比通常為5份傳導性碳:主要餘量之亦包括有標稱量之黏合劑或黏合材料(諸如NMP)之活性材料。黏合劑及碳傳導相之相對量可藉由在所提及活性材料之較大粒子之間產生一或多個導電路徑來指定。In the prior art, the particles are usually all deposited, such as being dropped into an existing current collector made of a metal foil such as copper, which includes a slurry-cast electrode. The slurry is usually prepared to contain an organic binder or binder material called NMP, used as a solvent in the petrochemical and plastic industries, and uses its non-volatile and ability to dissolve various materials. Compound. The ratio of active material to conductive carbon or carbon-based particles is usually 5 parts conductive carbon: the main balance also includes the active material with a nominal amount of binder or bonding material (such as NMP). The relative amounts of binder and carbon conductive phase can be specified by creating one or more conductive paths between the larger particles of the mentioned active material.

關於與二次電池中之黏合劑實施及使用相關之困難，研究已顯示，研發高效能電池系統需要自電極及電解質至黏合劑系統優化每一電池組件。然而，用於藉由將活性材料、非傳導性聚合物黏合劑以及傳導性添加劑之混合物澆鑄至金屬箔集電器上來製造電池電極之習知策略通常由於無規分佈之傳導相而導致電子或離子瓶頸及不良接觸，該等電子或離子瓶頸及不良接觸可為可能在陽極或陰極中觀測到之問題。且當高容量電極材料被採用時，在電化反應期間生成之高應力可能會破壞傳統黏合劑系統之機械完整性，導致電池循環壽命縮短。因此，對設計在不存在黏合劑使用之情況下展現結構完整性、可提供可靠、低阻力且連續內部空隙、微孔隙以及路徑以在電池充電-放電循環期間在需要時及在需要情況下保留活性材料且連接電極全部區域的新穎且穩健黏合劑系統或支架型以碳為主之電極結構存在關鍵需要。Regarding the difficulties associated with the implementation and use of adhesives in secondary batteries, research has shown that the development of high-efficiency battery systems requires optimization of each battery component from the electrode and electrolyte to the adhesive system. However, conventional strategies for manufacturing battery electrodes by casting a mixture of active materials, non-conductive polymer binders, and conductive additives onto metal foil current collectors usually result in electrons or ions due to randomly distributed conductive phases. Bottlenecks and poor contacts. These electronic or ionic bottlenecks and poor contacts may be problems that may be observed in the anode or cathode. And when high-capacity electrode materials are used, the high stress generated during the electrochemical reaction may damage the mechanical integrity of the traditional adhesive system, resulting in a shortened battery cycle life. Therefore, the design exhibits structural integrity without the use of adhesives, provides reliable, low resistance, and continuous internal voids, micropores, and paths to retain when and when needed during the battery charge-discharge cycle There is a key need for a novel and robust adhesive system or scaffold-type carbon-based electrode structure that is active material and connects all areas of the electrode.

與傳統舉動及解決與電池循環壽命縮短相關之黏合劑效能缺點形成對比，本發明所揭露之發明物質組成及物質產生方法(method/process)可消除： ●            黏合劑相之任何及全部形式；以及 ●            由較大以碳為主之粒子，諸如包括石墨及/或自石墨剝離提取或以其他方式產生之石墨烯形式之較大以碳為主之粒子界定之傳導相的潛在特定區域、特點及/或態樣。In contrast to traditional actions and solutions to the shortcomings of adhesive performance related to shortened battery cycle life, the inventive material composition and material production method (method/process) disclosed in the present invention can eliminate: ● Any and all forms of the adhesive phase; and ● Potential specific regions, characteristics, and characteristics of the conductive phase defined by larger carbon-based particles, such as graphite and/or graphene exfoliated from graphite or otherwise produced in the form of larger carbon-based particles / Or appearance.

此係藉由製造粒子來進行，在該粒子中多層石墨烯片之互連3D黏聚體熔合或燒結在一起，諸如無規地或以受控方向性(諸如正交)熔合或燒結在一起，或以其他方式聯接在一起，以充當一種類型之內部自撐式「黏合劑」或充當黏合劑置換物之接合材料，有效地允許消除獨立傳統黏合劑材料以達成實質性重量減輕。此類格式亦准許消除通常為許多電池之所需組件之獨立且專用集電器。黏合劑相及/或集電器之消除提供有益且所需特點，諸如： ●            具有允許質量可生產性之低每單位生產成本， ●            高可逆比容量， ●            低不可逆容量， ●            小粒度，諸如准許高通量/速率容量之小粒度， ●            用於便利整合及在商業電池應用中之使用之與常用電解質之相容性，以及 ●            跨任何數目之要求高之最終用途應用，包括汽車、飛機以及航天器之用於消費者效益之長充電-放電循環壽命。This is done by manufacturing particles in which interconnected 3D aggregates of multilayer graphene sheets are fused or sintered together, such as randomly or with controlled directionality (such as orthogonal). , Or otherwise connected together to act as a type of internal self-supporting "adhesive" or as a bonding material for adhesive replacement, effectively allowing the elimination of independent traditional adhesive materials to achieve substantial weight reduction. This type of format also allows the elimination of separate and dedicated current collectors that are usually required components for many batteries. The elimination of the binder phase and/or current collector provides beneficial and required features such as: ● Low per-unit production cost that allows quality and manufacturability, ● High reversible specific capacity, ● Low irreversible capacity, ● Small granularity, such as the small granularity that allows high throughput/rate capacity, ● Compatibility with common electrolytes to facilitate integration and use in commercial battery applications, and ● Across any number of demanding end-use applications, including long charge-discharge cycle life for consumer benefits in automobiles, airplanes, and spacecraft.

值得注意地，本文所揭露之技術產生出人意料之有利結果。其不需要傳統方法來諸如由石墨剝離產生石墨烯片且替代地由以大氣電漿為主之蒸氣流物料流合成一或多個多峰以碳為主之s。以碳為主之粒子之合成可正在運行地發生以由最初形成之以碳為主之均質成核進行成核或發生在直接沈積至支撐或犧牲基體上期間。因此，本發明所揭露之技術中之任一種或多種准許生長不依賴於傳統上所需之晶種粒子之裝飾以碳為主之結構，在該等裝飾以碳為主之結構上發生成核。It is worth noting that the technology disclosed in this article has produced unexpectedly beneficial results. It does not require traditional methods to generate graphene sheets from graphite exfoliation and instead synthesize one or more multi-peak carbon-based s from a vapor stream dominated by atmospheric plasma. The synthesis of carbon-based particles can occur on-the-fly with nucleation from the initially formed carbon-based homogeneous nucleation or during direct deposition onto a supporting or sacrificial substrate. Therefore, any one or more of the technologies disclosed in the present invention allow growth that does not depend on the traditionally required decoration of the seed particles with carbon-based structures, and nucleation occurs on the carbon-based decorations. .

在習知技術中，官能石墨烯之產生依賴於石墨作為起始材料之使用。為傳導材料之石墨已用作電池及其他電化學裝置中之電極。除其作為惰性電極之功能之外，已採用電化方法以形成石墨間夾化合物(GIC)且最近以將石墨剝離成少分層石墨烯。如一般所理解且如本文中所提及，剝離意指-在間夾化學物質相關情形下-材料層之完全分離且通常需要涉及高度極性溶劑及侵襲性試劑之侵襲性條件。電化方法具有吸引力，此係因為其消除化學氧化劑作為間夾或剝離之動力之使用，且用於可調諧GIC之電動力可控。更重要地，電化官能化及改質之廣泛能力能夠容易地合成官能石墨烯及其附加價值之奈米混成物。In the prior art, the production of functional graphene relies on the use of graphite as a starting material. Graphite, which is a conductive material, has been used as an electrode in batteries and other electrochemical devices. In addition to its function as an inert electrode, electrochemical methods have been used to form graphite intercalation compounds (GIC) and recently, graphite has been exfoliated into few-layered graphene. As generally understood and as mentioned herein, peeling means-in the case of intervening chemical substances-the complete separation of material layers and generally requires aggressive conditions involving highly polar solvents and aggressive reagents. The electrochemical method is attractive because it eliminates the use of chemical oxidizers as a force for pinching or stripping, and the electromotive force for tunable GIC is controllable. More importantly, the extensive capabilities of electrochemical functionalization and modification make it easy to synthesize functional graphene and its value-added nano-composites.

與剝離、用以產生石墨烯而包括石墨熱剝離不同，本發明所揭露之方法係關於一或多個包括碳之氣態物種，諸如包括甲烷(CH₄ )、流動至以微波為主之反應器或熱反應器之反應腔室中的包括碳之氣態物種。在接收能量，諸如由電磁輻射及/或熱能提供之能量時，進入氣態物種自發地裂解以與來自被供應至反應器中之額外氣態物種之其他經裂解碳一起形成同素異形體來產生初始以碳為主之位點，諸如所形成粒子，其具有以下或以其他方式促進以下： ●            由彼初始所形成粒子生長或去核缺陷之額外粒子；或 ●            正交熔合或燒結額外以碳為主之粒子，其中在用於碰撞粒子之碰撞點處存在足以組合之局域能量。系統結構 以碳為主之粒子 - 詳述 Unlike exfoliation, which is used to produce graphene and includes graphite thermal exfoliation, the method disclosed in the present invention relates to one or more gaseous species including carbon, such as methane (CH ₄ ), flowing to a microwave-based reactor Or gaseous species including carbon in the reaction chamber of a thermal reactor. When receiving energy, such as energy provided by electromagnetic radiation and/or thermal energy, the incoming gaseous species is spontaneously cracked to form an allotrope with other cracked carbon from the additional gaseous species supplied to the reactor to produce the initial Sites dominated by carbon, such as formed particles, have the following or otherwise promote the following: ● Extra particles for particle growth or de-nucleation defects formed by the original particles; or ● Orthogonal fusion or sintering with additional carbon as The main particle, in which there is enough local energy to combine at the collision point used to collide the particle. The system structure is mainly carbon particles - detailed

圖1A顯示具有於其中之可控電及離子傳導梯度之以碳為主之粒子100A，在其內本文所揭露之主題之各種態樣可被實施。以碳為主之粒子100A可經由不依賴於黏合劑之自裝配進行合成來以多峰尺寸為特點，該等多峰尺寸包括各種流孔、管道、空隙、路徑、管道或其類似者，以上任一者或多者經界定以具有特定尺寸，諸如為中孔。根據IUPAC命名法，中孔材料意指含有直徑介於2 nm與50 nm之間之孔隙之材料。出於比較之目的，IUPAC將微孔材料定義為具有直徑小於2 nm之孔隙之材料且將大孔材料定義為具有直徑大於50 nm之孔隙之材料。FIG. 1A shows a carbon-based particle 100A with a controllable electric and ion conduction gradient therein, in which various aspects of the subject matter disclosed herein can be implemented. The carbon-based particles 100A can be synthesized by self-assembly that does not rely on binders to feature multimodal sizes, which include various orifices, ducts, voids, paths, ducts, or the like, above Any one or more is defined to have a specific size, such as a mesopore. According to the IUPAC nomenclature, mesoporous materials refer to materials containing pores with diameters between 2 nm and 50 nm. For comparison purposes, IUPAC defines a microporous material as a material with pores with a diameter of less than 2 nm and a macroporous material as a material with pores with a diameter of greater than 50 nm.

中孔材料可包括各種類型之具有類似尺寸之中孔之二氧化矽及氧化鋁。鈮、鉭、鈦、鋯、鈰以及錫之中孔氧化物已被研究且報導。中孔材料、中孔碳(諸如碳及以碳為主之材料)之全部變型具有有至少一中孔尺寸之空隙、流孔、路徑、管道或其類似者，已達成特定***，直接應用於能量儲存裝置中。中孔碳可定義為具有介於中孔範圍內之孔隙度，且此顯著地增大比表面積。另一常用中孔材料為活性碳，該活性碳係指經處理以具有增大表面積之小、低體積孔隙之碳形式。在中孔情形下，活性碳通常由諸如視其合成條件而具有中孔隙度及微孔隙度之碳構架構成。根據IUPAC，中孔材料可在中層結構中無序或有序。在結晶無機材料中，中孔結構明顯地限制晶格單元數目，且此顯著地改變固態化學物質。舉例而言，中孔電活性材料之電池效能顯著地不同於其體結構之電池效能。The mesoporous material may include various types of silica and alumina with similarly sized mesopores. Niobium, tantalum, titanium, zirconium, cerium, and tin mesoporous oxides have been studied and reported. Mesoporous materials, all modifications of mesoporous carbon (such as carbon and carbon-based materials) have voids, orifices, paths, pipes or the like with at least one mesopore size, which have achieved specific uplifts and are directly applied Energy storage device. Mesoporous carbon can be defined as having a porosity in the mesoporous range, and this significantly increases the specific surface area. Another commonly used mesoporous material is activated carbon, which refers to a form of carbon that has been treated to have small, low-volume pores with increased surface area. In the case of mesoporous, activated carbon is usually composed of a carbon structure such as mesoporosity and microporosity depending on its synthesis conditions. According to IUPAC, mesoporous materials can be disordered or ordered in the mesostructure. In crystalline inorganic materials, the mesoporous structure obviously limits the number of lattice units, and this significantly changes the solid state chemical substance. For example, the battery performance of mesoporous electroactive materials is significantly different from the battery performance of its body structure.

如習知技術中所見，以碳為主之粒子100A在諸如甲烷(CH₄ )之試劑氣態物種之以大氣電漿為主之蒸氣流物料流中成核且生長以形成初始含碳及/或以碳為主之粒子且不特定地或明確地需要獨立單獨初始晶種粒子，在該獨立單獨初始晶種粒子周圍碳結構隨後生長。依照本發明所揭露之實施例，不依賴於獨立晶種粒子之初始以碳為主之合成粒子可隨後擴增： ●            諸如由圖1D中之顯微圖100D所示，正在運行地描述微波電漿反應腔室內依照由不依賴於衍生自進入含碳氣體空中之額外以碳為主之材料之晶種粒子的初始以碳為主之均質成核進行的成核及/或生長的系統聚結；或 ●            該擴增係藉由生長及/或直接沈積至熱反應器內諸如集電器之支撐或犧牲基體上來進行。 聚結意指其中同一組合物之二個相區域合在一起且形成更大相區域之方法。換言之，若可混溶物質之二個或更多個獨立塊體最少接觸則似乎將其彼此拉動在一起之方法。以碳為主之粒子100A可替代地僅稱為粒子及/或任何其他類似術語。如一般所理解且如本文所使用，根據國際純化學暨應用化學聯合會(IUPAC)命名法，術語中孔可定義為含有直徑介於2 nm與50 nm之間之孔隙之材料。As seen in the prior art, the carbon-based particles 100A nucleate and grow in the vapor stream of atmospheric plasma-based vapor stream of reagent gaseous species _{such as methane (CH 4) to form initial carbon and/or} Particles predominantly carbon do not specifically or explicitly require independent individual initial seed particles around which a carbon structure is subsequently grown. According to the disclosed embodiments of the present invention, the initial carbon-based synthetic particles that do not rely on independent seed particles can be subsequently amplified: The slurry reaction chamber is coalesced according to a system that does not rely on the initial carbon-based homogeneous nucleation of seed particles derived from additional carbon-based materials that enter the carbon-containing gas space. ; Or ● The amplification is carried out by growing and/or directly depositing on a support or sacrificial substrate such as a current collector in a thermal reactor. Coalescence refers to a method in which two phase regions of the same composition come together to form a larger phase region. In other words, if two or more independent blocks of miscible substances are in minimal contact, it seems a way to pull them together. The carbon-based particles 100A may alternatively be merely referred to as particles and/or any other similar terms. As generally understood and as used herein, according to the International Union of Pure and Applied Chemistry (IUPAC) nomenclature, the term mesopore can be defined as a material containing pores with a diameter between 2 nm and 50 nm.

在以微波為主之反應器(諸如反應器)中及/或以其他方式與其結合之反應腔室內以碳為主之粒子100A之合成及/或生長由2017年9月19日申請之Stowell等人,「Microwave Chemical Processing Reactor」，美國專利第9,767,992號揭露，該案以全文引用之方式併入本文中。合成可發生在除微波反應器以外之系統中，諸如發生在熱反應器中，該熱反應器一般指其中存在溫度相關化學反應器之由圍閉體積界定之化學反應器。The synthesis and/or growth of carbon-based particles 100A in a microwave-based reactor (such as a reactor) and/or in a reaction chamber combined with it in other ways was applied by Stowell, etc. on September 19, 2017 People, "Microwave Chemical Processing Reactor", disclosed in US Patent No. 9,767,992, which is incorporated herein by reference in its entirety. Synthesis can occur in systems other than microwave reactors, such as in thermal reactors, which generally refer to chemical reactors defined by enclosed volumes in which temperature-dependent chemical reactors exist.

以碳為主之粒子100A亦在圖1E中顯示為以碳為主之粒子100E，係如本文如此描述合成有包含短程局域奈米建構與長程近似碎形特點建構之組合之三維(3D)階層式結構，在此情形下其係指與彼此正交定位之連續層之形成。正交在此處定義為涉及各連續層相對於其下方一個層之90度旋轉，諸如此類，允許產生豎直或實質上豎直層及/或中間層。The carbon-based particle 100A is also shown in Fig. 1E as the carbon-based particle 100E, which is a three-dimensional (3D) structure composed of a combination of short-range local nanostructures and long-range similar fractal structures as described herein. Hierarchical structure, in this case, refers to the formation of continuous layers positioned orthogonal to each other. Orthogonality is defined here as referring to the 90 degree rotation of each successive layer relative to the layer below it, and so on, allowing vertical or substantially vertical layers and/or intermediate layers to be produced.

在用於鋰-硫(Li S)二次系統之電化電池陰極內適用於併有之相連微結構107F示於圖1F中，圖1F自身顯示示於圖1A及1E中之階層式孔隙101A之經放大且更詳細視圖。在一些實施方案中，如圖1A中所示，相連微結構107F之輪廓及形狀可結構上界定開放多孔支架102A及擴散路徑109F，該等擴散路徑109F適用於放電-充電循環期間自陽極至陰極之Li離子運輸。相連微結構107F可包括： ●            提供可調諧Li離子管道之由＞ 50 nm之尺寸101F界定之微孔構架，諸如擴散路徑109F； ●            充當於其中之用於快速Li離子運輸之Li離子高速通道之由約20 nm至約50 nm之尺寸101F界定(一般根據IUPAC命名法界定且稱為中孔或中孔的)之中孔通道；以及 ●            用於電荷收納及/或活性材料(諸如Li S系統中之硫(S))限制之由＜ 4 nm之尺寸103F界定之微孔織構，諸如孔隙105F。The connected microstructure 107F suitable for use in the cathode of an electrochemical battery used in a lithium-sulfur (Li S) secondary system is shown in FIG. Enlarged and more detailed view. In some embodiments, as shown in FIG. 1A, the contour and shape of the connected microstructure 107F can structurally define the open porous scaffold 102A and diffusion paths 109F, which are suitable for the discharge-charge cycle from anode to cathode Li ion transport. The connected microstructure 107F may include: ● Provide a tunable Li ion pipe with a microporous framework defined by a size of 101F> 50 nm, such as a diffusion path 109F; ● Mesoporous channels defined by 101F (generally defined according to IUPAC nomenclature and called mesopores or mesopores) with a size of 101F from about 20 nm to about 50 nm serving as the Li ion high-speed channel for rapid Li ion transport ;as well as ● A microporous texture defined by a size of 103F <4 nm, such as pores 105F, used for charge storage and/or restriction of active materials (such as sulfur (S) in the Li S system).

除提供用於限制活性材料且界定離子運輸路徑之孔隙105F之外亦包括擴散路徑109F之階層式多孔網狀結構100F可經組配以界定用於提供活性Li間夾結構之相連微結構107F。因此，具有以碳為主之粒子100E之階層式多孔網狀結構100F可實施於陽極或陰極或例如比容量定級在約744 mAh/g至約1,116 mAh/g之間之Li離子或Li S電池系統中。對於Li離子或Li S組配，諸如在經由毛細管灌注由熔融Li金屬提供時，Li可浸潤開放多孔支架以在反應系統中至少部分地與於其中之暴露碳發生化學反應。In addition to providing the pores 105F for confining the active material and defining the ion transport path, the hierarchical porous network structure 100F, which also includes the diffusion path 109F, can be configured to define the connected microstructure 107F for providing the active Li sandwich structure. Therefore, the hierarchical porous network structure 100F with carbon-based particles 100E can be implemented on the anode or cathode, or for example, Li ion or Li S whose specific capacity is rated between about 744 mAh/g and about 1,116 mAh/g. In the battery system. For Li ion or Li S combinations, such as when provided by molten Li metal via capillary infusion, Li can infiltrate the open porous scaffold to at least partially chemically react with exposed carbon in the reaction system.

以碳為主之粒子100A之一或多個物理、電學、化學及/或材料特性可在其合成期間被界定。此外，指要被引入化學材料中以更改其原始電學或光學特性之痕量雜質元素(諸如Si、SiO、SiO2、Ti、TiO、Sn、Zn及/或其類似物)之摻雜劑可在以碳為主之粒子100A合成期間動態併有以至少部分影響包括導電性、可濕性及/或經由階層式多孔網狀結構100F之離子傳導或運輸的材料特性。更一般而言，具有尺寸103F及/或階層式多孔網狀結構100F之微孔織構可經合成、製備或產生以包括用於諸如硫(S)之化學物質微米限制之較小孔隙，該等較小孔隙定義為介於1 nm至3 nm範圍內。此外，諸如示於圖1C中之各石墨烯片之直徑(L_a )可介於50 nm至200 nm範圍內。One or more of the physical, electrical, chemical, and/or material properties of the carbon-based particle 100A may be defined during its synthesis. In addition, dopants referring to trace impurity elements (such as Si, SiO, SiO2, Ti, TiO, Sn, Zn, and/or the like) that are to be introduced into chemical materials to modify their original electrical or optical properties can be used in The carbon-based particles 100A are dynamic during synthesis and have material properties that at least partially affect the conductivity, wettability, and/or ion conduction or transport through the hierarchical porous network structure 100F. More generally, a microporous texture having a size of 103F and/or a hierarchical porous network structure of 100F can be synthesized, prepared, or produced to include smaller pores for the micron confinement of chemical substances such as sulfur (S). Equally small pores are defined as being in the range of 1 nm to 3 nm. _{In addition, the diameter (L a} ) of each graphene sheet such as shown in FIG. 1C may be in the range of 50 nm to 200 nm.

開放多孔支架102A可不依賴於通常與傳導性添加劑結合使用之諸如傳統非傳導性聚合物黏合劑之黏合劑在電池最終用途應用中合成至金屬箔集電器上。涉及黏合劑使用之傳統組配可能由於無規分佈之傳導相而導致電子/電流傳導相關或離子收縮及不良接觸。此外，當高容量電極材料被採用時，在電化反應期間生成之相對高物理應力可能會破壞傳統黏合劑系統之機械完整性，因此之後縮短電池循環壽命。The open porous stent 102A can be synthesized on the metal foil current collector in the battery end-use application without relying on adhesives such as traditional non-conductive polymer adhesives commonly used in combination with conductive additives. Traditional combinations involving the use of adhesives may cause electron/current conduction correlation or ion shrinkage and poor contact due to randomly distributed conductive phases. In addition, when high-capacity electrode materials are used, the relatively high physical stress generated during the electrochemical reaction may destroy the mechanical integrity of the traditional adhesive system, thus shortening the battery cycle life afterwards.

用於合成以碳為主之粒子100A或為以碳為主之粒子100A或可與其一致之以碳為主之粒子100E之蒸氣流物料流可至少部分流動至電漿，諸如生成及/或流動至反應器及/或化學反應容器中之電漿的鄰近區域中。此類電漿反應器可經組配以朝向蒸氣流物料流傳送微波能量以至少部分輔助以碳為主之粒子100A之合成，可涉及由構成以碳為主之氣態物種(諸如甲烷(CH₄ ))進行之以碳粒子為主及/或碳粒子衍生之成核及生長，其中該成核及生長可在反應器內不依賴於晶種粒子由最初形成之以碳為主之均質成核實質上發生。此類反應器收納處於非平衡條件下之氣-固反應對照，其中氣-固反應可至少部分受以下中之任一者或多者控制： ●            與引入反應器中以合成以碳為主之粒子之構成以碳為主之氣態物種相關聯之游離電位及/或熱能；及/或 ●            與氣-固反應相關聯之動力學動量。 蒸氣流物料流可在實質上大氣壓下流動至反應器及/或反應腔室中以合成以碳為主之粒子100A。且以碳為主之粒子100A及/或諸如開放多孔支架102A之任何構成成員之可濕性變化至少部分可涉及與以碳為主之粒子100A相關聯之碳基質的極性調節。合成程序 微波反應器 The vapor stream used to synthesize carbon-based particles 100A or carbon-based particles 100A or the same carbon-based particles 100E can flow at least partially to the plasma, such as generation and/or flow To the vicinity of the plasma in the reactor and/or chemical reaction vessel. This type of plasma reactor can be configured to transmit microwave energy toward the vapor stream to at least partially assist the synthesis of carbon-based particles 100A, which may involve the formation of gaseous species (such as methane (CH ₄ )) Carrying out nucleation and growth based on carbon particles and/or derived from carbon particles, wherein the nucleation and growth can be performed in the reactor without relying on the homogenous nucleation of the seed particles from the initially formed carbon-based nucleation Essentially happened. This type of reactor contains a gas-solid reaction control under non-equilibrium conditions, where the gas-solid reaction can be controlled at least in part by any one or more of the following: ● With the introduction of the reactor to synthesize mainly carbon The composition of the particles is based on the free potential and/or heat energy associated with the gaseous species with carbon as the main component; and/or ● the dynamic momentum associated with the gas-solid reaction. The vapor stream can flow into the reactor and/or reaction chamber under substantially atmospheric pressure to synthesize carbon-based particles 100A. And the change in wettability of the carbon-based particles 100A and/or any constituent members such as the open porous scaffold 102A may at least partly involve the polarity adjustment of the carbon matrix associated with the carbon-based particles 100A. Synthesis program microwave reactor

包括諸如甲烷(CH₄ )之含碳構成物種之蒸氣流物料流可流動至以下二個一般類型反應器中之一個中以產生以碳為主之粒子100A： ●            熱反應器；或 ●            以微波為主之反應器。合適類型之微波反應器係由2017年9月19日申請之Stowell等人, 「Microwave Chemical Processing Reactor」，美國專利第9,767,992號揭露，該案以全文引用之方式併入本文中。The vapor stream including carbon-containing constituent species such as methane (CH ₄ ) can flow to one of the following two general types of reactors to produce carbon-based particles 100A: ● Thermal reactor; or ● Microwave The main reactor. A suitable type of microwave reactor is disclosed by Stowell et al., "Microwave Chemical Processing Reactor", US Patent No. 9,767,992, filed on September 19, 2017, which is incorporated herein by reference in its entirety.

術語正在運行意指新穎化學合成方法係基於接觸衍生自諸如含有甲烷(CH₄ )之流入含碳氣態物種之流入含碳氣態物種之顆粒材料以裂解該等氣態物種。如一般所理解且如本文中所提及，裂解意指用以在無難以解決之一氧化碳污染情況下且在實際上無二氧化碳排放物之情況下產生諸如高品質碳黑之元素碳及氫氣之甲烷熱解技術方法。可發生在微波反應器內以產生以碳為主之粒子100A之基礎吸熱反應顯示為以下方程式(7)： CH₄ + 74.85 kJ/mol ⟶ C + 2H₂ (7)The term running means that the novel chemical synthesis method is based on contacting _{particulate materials derived from the inflowing carbon-containing gaseous species such as methane (CH 4} ) containing inflowing carbon-containing gaseous species to crack the gaseous species. As generally understood and as mentioned herein, cracking means methane used to produce elemental carbon and hydrogen such as high-quality carbon black without difficult carbon monoxide pollution and virtually no carbon dioxide emissions. Pyrolysis technology method. The basic endothermic reaction that can occur in a microwave reactor to produce carbon-based particles 100A is shown as the following equation (7): CH ₄ + 74.85 kJ/mol ⟶ C + 2H ₂ (7)

衍生自上文所描述之裂解方法及/或類似或相異方法之碳可熔合在一起，同時分散於氣相中，稱為正在運行，以產生以碳為主之粒子、結構、實質上2D石墨烯片、3D黏聚體及/或界定於其中之路徑，包括： ●            如圖1C中示意性地描繪熔合在一起以形成促進沿且跨如圖1B中所示之石墨烯片101C接觸點之導電之開放多孔支架102A的多層石墨烯片101C之互連3D黏聚體101B及/或單層石墨烯可包括且/或指以堆疊組配定向以具有稱為堆疊高度(Lc)之豎直高度的5至15層少層石墨烯；以及 ●            與互連3D黏聚體101B一起散佈或以其他方式由其界定形狀之相連微結構107F中之任一個或多個；在一些組配中，互連3D黏聚體可經製備以包含單層石墨烯(SLG)、定義為介於5至15層石墨烯範圍內之少層石墨烯(FLG)或多層石墨烯(MLG)中之一或多者。The carbon derived from the cracking method described above and/or similar or different methods can be fused together and dispersed in the gas phase at the same time, called running, to produce carbon-based particles, structures, and essentially 2D Graphene sheets, 3D adhesives and/or paths defined in them include: ● Interconnect 3D adhesion of multilayer graphene sheets 101C that are fused together to form an open porous scaffold 102A that promotes conduction along and across the contact points of the graphene sheet 101C as shown in Fig. 1B are depicted schematically in Fig. 1C The body 101B and/or single-layer graphene may include and/or refer to 5 to 15 layers of few-layer graphene oriented in a stacked configuration to have a vertical height called stack height (Lc); and ● Any one or more of the connected microstructures 107F dispersed with the interconnected 3D cohesive body 101B or otherwise defined by the shape; in some configurations, the interconnected 3D cohesive body can be prepared to contain a single Layered graphene (SLG) is defined as one or more of few-layer graphene (FLG) or multilayer graphene (MLG) within the range of 5 to 15-layer graphene.

如先前所介紹，多層石墨烯片之互連3D黏聚體101B正交熔合在一起以充當一種類型之內部自撐式黏合劑或接合材料，允許消除獨立傳統黏合劑材料。如通常所理解且如本文中所提及，該等程序實質上不同於習知燒結或焙燒，此意指藉由熱或壓力壓緊且形成材料固體塊體且不使其熔融至其中材料在特定銳角下彼此接合之液化點的方法。As previously introduced, the interconnected 3D adhesives 101B of the multilayer graphene sheets are orthogonally fused together to act as a type of internal self-supporting adhesive or bonding material, allowing the elimination of independent traditional adhesive materials. As generally understood and as mentioned herein, these procedures are substantially different from conventional sintering or firing, which means that a solid mass of material is formed by pressing heat or pressure without melting the material in it. The method of the liquefaction point that joins each other at a specific acute angle.

在本文中定義為介於5至15層石墨烯片範圍內之少層石墨烯(FLG)隨時間推移在相對於其他FLG片而言不平之角度下熔合以在一定角度下成核且/或生長且因此自裝配。此外，處理條件可經調諧以達成以碳為主之粒子100A，亦指多個以碳為主之粒子在反應腔室內之組件及/或壁表面上或在與其他以碳為主之材料接觸時完全正在運行之合成、成核及/或生長。Defined herein as the few-layer graphene (FLG) in the range of 5 to 15-layer graphene sheets that fuse over time at an uneven angle relative to other FLG sheets to nucleate at a certain angle and/or Grows and therefore self-assembles. In addition, the processing conditions can be tuned to achieve 100A of carbon-based particles, which also refers to multiple carbon-based particles on components and/or wall surfaces in the reaction chamber or in contact with other carbon-based materials Synthesis, nucleation, and/or growth are completely running at all times.

沈積碳及/或以碳為主之材料之導電性可藉由向沈積相之第一部分中之碳相中添加金屬添加物來加以調諧或經調諧以改變所論述之各種粒子之比率。其他參數及/或添加物可作為高能沈積方法之一部分來加以調節以使得一定能量度之沈積碳及/或以碳為主之粒子將： ●            結合在一起；或 ●            不結合在一起。The conductivity of deposited carbon and/or carbon-based materials can be tuned by adding metal additives to the carbon phase in the first part of the deposited phase or tuned to change the ratio of the various particles in question. Other parameters and/or additives can be adjusted as part of the high-energy deposition method so that the deposited carbon and/or carbon-based particles of a certain degree of energy will: ● combined together; or ● Not combined.

藉由在以大氣電漿為主之蒸氣流物料流中使以碳為主之粒子100A正在運行地成核及/或生長、或直接成核及/或生長至支撐或犧牲基體上，在傳統電池及傳統電池製造方法中發現之大量步驟及組分可被消除。此外，大量調適及可調諧性可被啟用或以其他方式添加至所論述之碳及/或以碳為主之材料中。By nucleating and/or growing, or directly nucleating and/or growing carbon-based particles 100A on a supporting or sacrificial substrate in a vapor stream material stream dominated by atmospheric plasma, the traditional A large number of steps and components found in batteries and traditional battery manufacturing methods can be eliminated. In addition, a large amount of adaptability and tunability can be enabled or otherwise added to the carbon and/or carbon-based materials discussed.

舉例而言，傳統電池可使用活性材料、石墨等之起始存料，該起始存料可作為要被混合至漿料中之現成材料獲得。相比之下，本文所揭露之以碳為主之粒子100A可能夠進行作為碳或以碳為主之材料合成及/或沈積過程之一部分之材料特性即時調適及/或調諧，此時該等材料正在運行地合成且/或沈積至基體上。關於二次電池領域中以碳為主之支架型電極材料產生，此能力與當前可獲得之能力呈現出乎意料、出人意料且實質上有利之偏離。For example, a traditional battery can use a starting stock of active material, graphite, etc., which can be obtained as a ready-made material to be mixed into the slurry. In contrast, the carbon-based particles 100A disclosed in this article may be capable of real-time adjustment and/or tuning of the material properties as part of the carbon or carbon-based material synthesis and/or deposition process. The material is being synthesized on the fly and/or deposited onto the substrate. Regarding the production of carbon-based stent-type electrode materials in the field of secondary batteries, this capability presents an unexpected, unexpected, and substantially beneficial deviation from the currently available capability.

2017年9月19日申請之Stowell等人, 「Microwave Chemical Processing Reactor」，美國專利第9,767,992號所揭露之反應器及/或反應器設計可經調節、組配及/或調適以控制暴露於諸如甲烷(CH₄ )之以碳為主之氣態原料物種之反應腔室內表面上需要或不合需要之成核位點。正在運行之粒子品質可受其在氣態物種中之溶解度影響，在該氣態物種中其流動以使得一旦達成特定能量位準，則如藉由熱裂解所描述，碳在微波反應器中裂解掉且形成其自身固體並非難以想像。 調節反應腔室壁上不合需要之碳積聚 Stowell et al., "Microwave Chemical Processing Reactor", filed on September 19, 2017, the reactor and/or reactor design disclosed in US Patent No. 9,767,992 can be adjusted, configured and/or adapted to control exposure to such Required or undesirable nucleation sites on the surface of the reaction chamber of the gaseous feedstock species of methane (CH _{4 ), which is mainly carbon.} The quality of running particles can be affected by their solubility in gaseous species, where they flow so that once a specific energy level is reached, as described by thermal cracking, carbon is cracked in a microwave reactor and The formation of its own solid is not unimaginable. Regulate undesirable carbon accumulation on the wall of the reaction chamber

此外，所揭露之反應器及相關系統之調諧可被執行以諸如在觀測非所需處理條件之前主動地且諸如在觀測該等條件之後被動地解決與以碳為主之微波反應器阻塞相關聯之問題。舉例而言，開放表面、進料孔、軟管、管路及/或其類似者可積聚作為所執行合成程序之副產物的不合需要之以碳為主之顆粒物質以產生以碳為主之粒子100A。在微波反應器中觀測到之中心問題可包括此經歷流孔中及/或沿流孔之阻塞之傾向，原因與暴露於亦具有碳溶解度之流動中氣態含碳物種之壁及其他表面相關。因此，在反應腔室壁上及/或在出口管上不合需要地生長為有可能的。隨時間推移，彼等生長向外延伸且最終撞擊流且可關閉在反應器及/或反應腔室內發生之化學反應。此類現象可類似於管狀物，諸如高效能或快速運轉內燃機中燒油之廢氣、壁堆積物，其中代替灼燒(諸如燃燒)以化石燃料為主之汽油，使用甲烷以在反應腔室孔上產生不合需要之碳沈積物，此係因為反應腔室內部金屬自身具有碳溶解度位準。In addition, the tuning of the disclosed reactor and related systems can be performed such as to actively resolve undesired processing conditions before observing the undesired processing conditions and such as to passively resolve the obstruction associated with carbon-based microwave reactors after observing such conditions. The problem. For example, open surfaces, feed holes, hoses, pipes, and/or the like can accumulate undesirable carbon-based particulate matter as a by-product of the synthesis process performed to produce carbon-based particulate matter. Particle 100A. Central problems observed in microwave reactors may include this tendency to experience blockage in and/or along the orifice, due to exposure to walls and other surfaces of gaseous carbon-containing species in the flow that also have carbon solubility. Therefore, undesirable growth on the wall of the reaction chamber and/or on the outlet pipe is possible. Over time, they grow outward and eventually impinge on the stream and can shut down the chemical reactions occurring in the reactor and/or reaction chamber. This kind of phenomenon can be similar to tubes, such as high-efficiency or fast-running internal combustion engine burning exhaust gas, wall deposits, in which instead of burning (such as burning) fossil fuel-based gasoline, methane is used in the reaction chamber hole Undesirable carbon deposits are generated on the surface because the metal inside the reaction chamber has its own carbon solubility level.

儘管甲烷主要用於產生以碳為主之粒子100A，但任何含碳及/或烴氣如C₂ 或乙炔或C₂ H₂ 、CH₄ 、丁烷、天然氣、生物氣體(諸如衍生自生物物質分解之生物氣體)中之任一者或多者同樣用以提供含碳源。Although methane is mainly used to produce carbon-based particles 100A, any carbon-containing and/or hydrocarbon gas such as C ₂ or acetylene or C ₂ H ₂ , CH ₄ , butane, natural gas, biogas (such as derived from biomass) Any one or more of the decomposed biogas) is also used to provide a carbon-containing source.

所描述之不可控且不合需要之微波反應器暴露表面內碳生長可與發生在發動機之如與氣缸內徑相對之內燃機廢氣歧管內之碳生長進行比較，尤其其中諸如將進入電漿相中之熱及經激發氣體之電漿羽處於歧管起點處，且灼燒氣體及以碳為主之片段向下行進且向上***流過歧管、交叉管道及催化轉化器以及出口管道。因此，處理條件可主動經調諧以調節且因此收納微波反應器中之潛在碳堆積物，此舉依賴於用於烴氣裂解之電漿存在。為維持此電漿，必須維持特定條件集合，在其他方面背壓積聚可能會在其產生及後續引燃之前破壞電漿等。 熱反應器 The described uncontrollable and undesirable carbon growth in the exposed surface of the microwave reactor can be compared with the carbon growth that occurs in an engine such as the exhaust manifold of an internal combustion engine opposite to the inner diameter of the cylinder, especially where such as will enter the plasma phase The plasma plume of the heat and excited gas is at the beginning of the manifold, and the burning gas and the carbon-based fragments travel downwards and upwards are inserted through the manifolds, cross pipes, catalytic converters, and outlet pipes. Therefore, the processing conditions can be actively tuned to adjust and thus accommodate potential carbon deposits in the microwave reactor, which depends on the presence of plasma for hydrocarbon gas cracking. In order to maintain this plasma, a certain set of conditions must be maintained. In other respects, the accumulation of back pressure may destroy the plasma before it is generated and subsequently ignited. Thermal reactor

在微波反應器中以碳為主之粒子100A之合成之替代方案或附加方案中，結構化碳可藉由在諸如熱反應器之反應器中藉由熱應用進行烴熱裂解來產生。例示性組配可包括諸如前述烴中之任一者或多者之進入以碳為主之氣態物種對類似於燈泡中之金屬絲之加熱元件的暴露。In an alternative or additional solution to the synthesis of carbon-based particles 100A in a microwave reactor, structured carbon can be produced by thermally cracking hydrocarbons by thermal application in a reactor such as a thermal reactor. Exemplary configurations may include the exposure of a gaseous species predominantly carbon, such as any one or more of the aforementioned hydrocarbons, to a heating element similar to the wire in a light bulb.

加熱元件使其中進入含碳氣體被電離之反應腔室內部變熱。含碳氣體由於不存在足以維持燃燒之氧氣而不灼燒，但相反地由與諸如呈熱形式之進入熱輻射接觸而電離，以引起以碳為主之粒子100A之構成成員成核，且最終經由成核來合成以碳為主之粒子100A及/或整體類似於其之以碳為主之粒子。在熱反應器中，所觀測到之以碳為主之粒子成核中之至少一些可發生在壁上或加熱元件自身上。儘管如此，足夠小以藉由流動氣體速度裂解之粒子仍可成核，其中該等粒子被捕獲以輔助以碳為主之粒子100A之產生。The heating element heats the inside of the reaction chamber in which the carbon-containing gas is ionized. Carbon-containing gas does not burn because there is no oxygen sufficient to maintain combustion, but instead is ionized by contact with incoming thermal radiation, such as heat, to cause nucleation of the constituent members of carbon-based particles 100A, and finally Through nucleation, the carbon-based particles 100A are synthesized and/or the carbon-based particles are generally similar to the carbon-based particles. In the thermal reactor, at least some of the observed nucleation of carbon-based particles can occur on the wall or on the heating element itself. Nonetheless, particles that are small enough to be split by the velocity of the flowing gas can still nucleate, and the particles are captured to assist the production of carbon-based particles 100A.

經裂解碳可用於產生多殼富勒烯碳奈米洋蔥(carbon nano-onion，CNO)及/或其他富勒烯以及具有富勒烯內部結晶學之碳之較小溶離份。在比較經由微波及熱反應器進行之以碳為主之粒子100A之合成中，已觀測到以下區別： ●            微波反應器可提供適合於提供較寬範圍之碳同素異形體之調諧能力；而 ●            熱反應器傾向於允許微調諸如熱流量、溫度及/或其類似者之過程參數以達成以碳為主之粒子100A之特定最終用途應用目標之需要。The cracked carbon can be used to produce multi-shell fullerene carbon nano-onion (CNO) and/or other fullerenes, as well as smaller dissociated fractions of carbon with internal fullerene crystallography. In comparing the synthesis of carbon-based particles 100A through microwave and thermal reactors, the following differences have been observed: ● Microwave reactors can provide tuning capabilities suitable for providing a wide range of carbon allotropes; and ● Thermal reactors tend to allow fine-tuning of process parameters such as heat flow, temperature, and/or the like to achieve the specific end-use application goals of carbon-based particles 100A.

舉例而言，熱反應器當前用於構建諸如陽極及陰極之Li S電化電池電極。典型處理過程溫度介於成千上萬絕對溫度(Kelvin)範圍內，以產生在被壓縮時導電性大於500 S/m或大於5,000 S/m或為500 S/m至20,000 S/m之以碳為主之粒子100A及/或與其相關之以碳為主之聚集體。最佳效能已被觀測到介於2,000-4,000 K之間。 以碳為主之粒子 - 物理特性及於 Li 離子及 Li S 電池中之實施 For example, thermal reactors are currently used to construct LiS electrochemical battery electrodes such as anodes and cathodes. The typical processing temperature is in the range of thousands of absolute temperatures (Kelvin) to produce a conductivity greater than 500 S/m or greater than 5,000 S/m or between 500 S/m and 20,000 S/m when compressed Carbon-based particles 100A and/or related carbon-based aggregates. The best performance has been observed to be between 2,000-4,000 K. Carbon-based particles - physical properties and implementation in Li ion and Li S batteries

示於圖1A-1F中之以碳為主之結構中之任一個可被併入二次電池電極，諸如鋰(Li)離子電池之電極中，此係如2019年6月6日公開之Lanning等人, 「Lithium Ion Battery and Battery Materials」，美國專利公開案第2019/0173125號實質上所闡述，該案以全文引用之方式併入本文中。所揭露之實施方案通常關於陽極內之Li併有或灌注，但以碳為主之系統可針對與陰極，尤其其中需要S微米限制以減少不合需要之聚硫化物(PS)穿梭及電池自放電之Li S系統中之陰極的相容性及整合來加以修改。Any of the carbon-based structures shown in Figures 1A-1F can be incorporated into secondary battery electrodes, such as those of lithium (Li) ion batteries, such as Lanning published on June 6, 2019. Et al., "Lithium Ion Battery and Battery Materials", U.S. Patent Publication No. 2019/0173125 is essentially set forth, which is incorporated herein by reference in its entirety. The disclosed embodiments generally involve the coexistence or perfusion of Li in the anode, but the carbon-based system can be targeted at the cathode, especially where the S micron limit is required to reduce undesirable polysulfide (PS) shuttle and battery self-discharge The compatibility and integration of the cathode in the Li S system can be modified.

含於以碳為主之粒子100A中且/或以其他方式與其相關聯之顆粒碳可在Li離子電池陽極或陰極中作為結構及/或導電材料來實施且特徵在於具有廣泛孔徑分佈，亦稱為多峰孔隙尺寸分佈之階層式多孔網狀結構100F。舉例而言，除如圖1F中所示之相連微結構107F之外或作為其替代物，顆粒碳可含有至少部分進一步界定具有一或多個擴散路徑109F之開放多孔支架102A之多峰分佈之孔隙。該等孔隙之尺寸可為0.1奈米至10奈米、10奈米至100奈米、100奈米至1微米及/或大於1微米。孔結構可含有具有多峰尺寸分佈之孔隙，包括尺寸為1 nm至4 nm之較小孔隙及尺寸為30 nm至50 nm之較大孔隙。以碳為主之粒子100A中之此類多峰孔隙尺寸分佈可在Li S電池系統組配中有益，其中Li S電池中之含S陰極可被限制在具有尺寸為約小於1.5 nm或介於1 nm至4 nm範圍內之尺寸103F之孔隙105F中。在尺寸介於30 nm至50 nm範圍內之較大孔隙或路徑或尺寸大於溶劑化鋰離子二倍之孔隙中包括相連微結構107F之以碳為主之陰極中S及/或所生成S化合物的飽和度及結晶度控制可致能且/或促進溶劑化Li離子在陰極中的快速擴散或質量轉移。The particulate carbon contained in the carbon-based particle 100A and/or otherwise associated with it can be implemented as a structural and/or conductive material in the anode or cathode of a Li-ion battery and is characterized by having a wide pore size distribution, also known as It is a hierarchical porous network structure 100F with multimodal pore size distribution. For example, in addition to or as an alternative to the connected microstructure 107F as shown in FIG. 1F, the particulate carbon may contain at least part of the multimodal distribution that further defines the open porous scaffold 102A with one or more diffusion paths 109F Pores. The size of the pores may be 0.1 nanometers to 10 nanometers, 10 nanometers to 100 nanometers, 100 nanometers to 1 micrometer, and/or greater than 1 micrometer. The pore structure may contain pores with a multimodal size distribution, including smaller pores with a size of 1 nm to 4 nm and larger pores with a size of 30 nm to 50 nm. Such a multimodal pore size distribution in 100A of carbon-based particles can be beneficial in the assembly of Li S battery systems, where the S-containing cathode in Li S batteries can be restricted to have a size of about less than 1.5 nm or between In the pore 105F of size 103F in the range of 1 nm to 4 nm. S and/or formed S compounds in a carbon-based cathode containing connected microstructure 107F in larger pores or paths or pores with a size in the range of 30 nm to 50 nm or twice the size of the solvated lithium ion The control of saturation and crystallinity of ZnO can enable and/or promote the rapid diffusion or mass transfer of solvated Li ions in the cathode.

如先前所介紹，縮寫為Li-S電池之鋰硫電池為一種類型之可充電電池，因其高比能而著名。Li-S電池可包括經浸潤或灌注以限制在孔隙105F內及沿中孔粒子100E之相連微結構107F之暴露表面限制的硫(S)。因此，S可在被併入Li S電池之陰極中時浸潤開放多孔支架102A以在以碳為主之粒子100A、100E之內表面上及/或在相連微結構107F內沈積，此係如圖1F中及由圖1G中所示之示意圖100G所示，該示意圖100G顯示與硫還原成硫離子(S^2- )相關聯之中間步驟。 以碳為主之粒子 - 經 形成以解決聚硫化物 ( PS ) 相關挑戰 As previously introduced, the lithium-sulfur battery abbreviated as Li-S battery is a type of rechargeable battery, which is famous for its high specific energy. The Li-S battery may include sulfur (S) that is infiltrated or poured to confine within the pores 105F and along the exposed surface of the connected microstructure 107F of the mesoporous particles 100E. Therefore, S can infiltrate the open porous scaffold 102A when it is incorporated into the cathode of the Li S battery to deposit on the inner surface of the carbon-based particles 100A, 100E and/or in the connected microstructure 107F, as shown in Fig. In 1F and shown by the schematic diagram 100G shown in FIG. 1G, the schematic diagram 100G shows the intermediate steps associated with the ^{reduction of sulfur to sulfide ions (S 2- ).} The carbon-based particles - formed to solve a polysulfide (PS) associated challenges

試圖解決與該等聚硫化物(PS)系統相關聯之挑戰中之至少一些，以碳為主之粒子100A及陰極活性材料形成變形球粒子(meta-particle)構架，其中諸如可形成如圖1G中所示之PS化合物100G之元素硫之陰極電活性材料被佈置在碳孔隙/通道內，諸如如圖1F中所示之相連微結構107F中之任一個或多個，包括孔隙104F、105F及/或路徑106F及/或擴散路徑109F內。舉例而言，S可以表示總重量/體積之以碳為主之粒子100A及/或100E總體中之活性材料之35-100%的負載位準實質上併在相連微結構107F內。In an attempt to solve at least some of the challenges associated with these polysulfide (PS) systems, the carbon-based particles 100A and the cathode active material form a meta-particle framework, such as those shown in Figure 1G The cathode electroactive material of element sulfur of the PS compound 100G shown in is arranged in the carbon pores/channels, such as any one or more of the connected microstructures 107F as shown in FIG. 1F, including pores 104F, 105F and In/or path 106F and/or diffusion path 109F. For example, S can indicate that the loading level of 35-100% of the active material in the total weight/volume of the carbon-based particles 100A and/or 100E is substantially within the connected microstructure 107F.

此類型之經組織粒子構架可在諸如元素S之絕緣陰極電活性材料與集電器之間提供低阻力電接觸，同時提供相對高暴露表面積結構，該等相對高暴露表面積結構對總體比容量有益且可輔助如藉由形成暫時保留在相連微結構107F中，諸如孔隙105F中之Li S化合物而增強之Li離子微米限制，以之後控制且導引如可與電池電極及/或系統中之電流傳導相關的Li離子遷移。以碳為主之粒子100A之實施亦可藉由經由使用經調適結構，諸如藉由相連微結構107F所示之經調適結構以有效防止其不合需要地遷移通過電解質到達陽極，產生與電池自放電相關聯之不合需要寄生化學反應來捕集任何所產生聚硫化物之至少某一部分而益於陰極以及陽極穩定性。 Li S 電池系統使用期間聚硫化物 ( PS ) 之 遷移 This type of organized particle framework can provide a low-resistance electrical contact between an insulated cathode electroactive material such as element S and a current collector, while providing a relatively high exposed surface area structure, which is beneficial to the overall specific capacity and It can assist, for example, the enhanced Li ion micro-confinement by forming the Li S compound temporarily retained in the connected microstructure 107F, such as the pore 105F, so as to control and guide the current conduction in the battery electrode and/or system afterwards. Related Li ion migration. The carbon-based particle 100A can also be implemented by using an adapted structure, such as the adapted structure shown by the connected microstructure 107F, to effectively prevent it from undesirably migrating through the electrolyte to the anode, resulting in self-discharge of the battery The associated undesirable need for a parasitic chemical reaction to trap at least a portion of any polysulfide produced to benefit cathode and anode stability. Polysulfide (PS) of the system during Li S cell migration

如先前所介紹，參照在Li S電池電極及/或系統中所觀測到之PS穿梭機制，PS很好地溶解於電解質中。此舉使另一Li-S電池具有特徵，亦即穿梭機制。在陰極處形成且溶解之PS S_n2 擴散至Li陽極且還原成Li₂ S₂ 及Li₂ S。在放電期間在陰極處形成之PS物種S_n ^2- 溶解於此處電解質中。相對於陽極之濃度梯度發展，此舉使PS朝向陽極擴散。PS逐步分佈在電解質中。後續高級PS物種與此等化合物反應且形成低級聚硫化物S_(n-x) 。此意謂陰極處硫之所需化學反應亦部分以不受控方式發生在其中可想像化學反應及電化反應之陽極處，此舉負面地影響總體電池特徵。As previously introduced, referring to the PS shuttle mechanism observed in LiS battery electrodes and/or systems, PS is well dissolved in the electrolyte. This move gives another Li-S battery a characteristic, that is, a shuttle mechanism. _{The PS S n2} formed and dissolved at the cathode diffuses to the Li anode and is reduced to Li ₂ S ₂ and Li ₂ S. _{The PS species S n} ^2- formed at the cathode during discharge is dissolved in the electrolyte here. With respect to the development of the concentration gradient of the anode, this action causes the PS to diffuse toward the anode. PS is gradually distributed in the electrolyte. Subsequent high-level PS species react with these compounds and form low-level polysulfide S _(nx) . This means that the required chemical reaction of sulfur at the cathode also partly occurs in an uncontrolled manner at the anode where chemical and electrochemical reactions can be imagined, which negatively affects the overall battery characteristics.

若低級PS物種在陽極附近形成，則其擴散至陰極。當電池放電時，此等經擴散物種進一步還原成Li₂ S₂ 或Li₂ S。因此，在放電過程或更確切而言電池自放電期間，陰極反應部分發生在陽極處。二者均為減小比容量之非所需效應。相比之下，充電過程期間向陰極之擴散之後為PS物種自低級至高級之再氧化。隨後，此等PS再次擴散至陽極。此循環一般稱為可極為明顯之穿梭機制，有可能地，電池可接受無限電荷發生化學短路。一般而言，穿梭機製造成寄生硫活性物質損失。此係由於陰極區域外部之Li₂ S₂ 及Li₂ S之不受控分離且其最終造成電池循環能力大大減弱且使用壽命大大縮短。另外老化機制可為因電池反應期間體積變化所致之陰極上Li₂ S₂ 及Li₂ S之非均質分離或機械陰極結構***。 以碳為主之粒子之孔隙限制硫且防止 PS 穿梭至陽極 If low-level PS species are formed near the anode, they diffuse to the cathode. When the battery is discharged, these diffused species are further reduced to Li ₂ S ₂ or Li ₂ S. Therefore, during the discharge process or more precisely during the self-discharge of the battery, the cathode reaction partly occurs at the anode. Both are undesirable effects of reducing the specific capacity. In contrast, diffusion to the cathode during the charging process is followed by re-oxidation of PS species from low to high levels. Subsequently, these PS diffuse to the anode again. This cycle is generally called a very obvious shuttle mechanism. It is possible that the battery can accept an infinite charge to cause a chemical short circuit. Generally speaking, the shuttle mechanism causes the loss of parasitic sulfur active substances. This is due to the _{uncontrolled separation of Li 2} S ₂ and Li ₂ S outside the cathode region, which ultimately results in a greatly reduced battery cycle capacity and a greatly shortened service life. _{In addition, the aging mechanism can be the heterogeneous separation of Li 2} S ₂ and Li ₂ S on the cathode due to the volume change during the battery reaction or the mechanical cathode structure split. The pores of carbon-based particles limit sulfur and prevent PS from shuttle to the anode

為解決PS穿梭現象，陰極中之以碳為主之粒子100A之相連微結構107F中之任一個或多個可提供形成有適當尺寸之區域，諸如具有小於1.5 nm之尺寸103F之孔隙105F，以驅動諸如S及Li₂ S之低級聚硫化物之產生，且因此防止促進Li穿梭(諸如對陽極之損失)之高級可溶聚硫化物Li_x S_y (其中y大於3)之形成。如本文所描述，顆粒碳及陰極材料混合物之結構可在顆粒碳形成於微波電漿或熱反應器內期間經調諧。另外，與Li相形成相關之諸如元素硫之陰極電活性材料溶解度及結晶度可被限制在以碳為主之粒子100A之相連微結構107F之微孔及/或中孔構架內/在其內被捕集。In order to solve the PS shuttle phenomenon, any one or more of the connected microstructures 107F of the carbon-based particles 100A in the cathode can provide a region with an appropriate size, such as a pore 105F with a size of 103F less than 1.5 nm, to Drives the production of low-level polysulfides such as S and Li _{2 S, and thus prevents the formation of high-level soluble polysulfides Li x} S _y (where y is greater than 3) that promote Li shuttle (such as loss to the anode). As described herein, the structure of the particulate carbon and cathode material mixture can be tuned during the formation of the particulate carbon in the microwave plasma or thermal reactor. In addition, the solubility and crystallinity of cathode electroactive materials such as elemental sulfur related to the formation of the Li phase can be limited to the micropores and/or mesoporous frameworks of the connected microstructure 107F of the carbon-based particles 100A. Was arrested.

多峰孔隙尺寸分佈可指示結構具有高表面積及大量小孔隙，該等小孔隙係經由具有較大特點尺寸以提供較多通過結構之傳導路徑之結構中材料有效地連接至基體及/或集電器。該等結構之一些非限制性實例為具有由大致圓柱形及/或球面孔隙及/或粒子構成之不同尺寸之互連通道的碎形結構、樹枝狀結構、分支結構以及聚集結構。The multimodal pore size distribution can indicate that the structure has a high surface area and a large number of small pores. The small pores are effectively connected to the substrate and/or current collector through the material in the structure that has a larger characteristic size to provide more conductive paths through the structure . Some non-limiting examples of such structures are fractal structures, dendritic structures, branch structures, and aggregated structures with interconnecting channels of different sizes composed of substantially cylindrical and/or spherical pores and/or particles.

本文所描述之Li離子或Li S電池中所使用之例示性顆粒碳材料描述於名為「Seedless Particles with Carbon Allotropes」之美國專利第9,997,334號中，該案被讓與本申請案同一受讓人且以引用之方式併入本文中。顆粒碳材料可含有包括多個碳聚集體之以石墨烯為主之碳材料，各碳聚集體具有多個碳奈米粒子，各碳奈米粒子包括石墨烯，任擇地包括多壁球面富勒烯；且任擇地不具有晶種粒子，諸如不具有成核粒子。在一些情況下，顆粒碳材料亦在不使用催化劑之情況下產生。以石墨烯為主之碳材料中之石墨烯具有至多15個層。碳聚集體中碳與氫除外之其他元素之比大於99%。碳聚集體之中值尺寸為1微米至50微米或0.1微米至50微米。當使用布厄特(Brunauer-Emmett-Teller，BET)法且利用氮氣作為吸附物來量測時，碳聚集體之表面積為至少10 m² /g或至少50 m² /g或為10 m² /g至300 m² /g或為50 m² /g至300 m² /g。當被壓縮時，碳聚集體具有大於500 S/m或大於5,000 S/m或500 S/m至20,000 S/m之導電性。 以碳為主之粒子與習知技術之間之區別 Exemplary particulate carbon materials used in Li ion or Li S batteries described herein are described in US Patent No. 9,997,334 entitled "Seedless Particles with Carbon Allotropes", which is assigned to the same assignee as this application And incorporated into this article by reference. The particulate carbon material may include a graphene-based carbon material including a plurality of carbon aggregates. Each carbon aggregate has a plurality of carbon nanoparticles. Each carbon nanoparticle includes graphene, optionally including a multi-walled spherical surface. Leene; and optionally no seed particles, such as no nucleating particles. In some cases, particulate carbon materials are also produced without the use of catalysts. Graphene in graphene-based carbon materials has at most 15 layers. The ratio of carbon to other elements other than hydrogen in the carbon aggregate is greater than 99%. The median size of the carbon aggregates is from 1 micrometer to 50 micrometers or from 0.1 micrometer to 50 micrometers. When the Brunauer-Emmett-Teller (BET) method is used and nitrogen is used as an adsorbent for measurement, the surface area of the carbon aggregate is at least 10 m ² /g or at least 50 m ² /g or 10 m ² /g to 300 m ² /g or 50 m ² /g to 300 m ² /g. When compressed, the carbon aggregate has a conductivity of greater than 500 S/m or greater than 5,000 S/m or 500 S/m to 20,000 S/m. The difference between carbon-based particles and conventional technology

習知複合材料型Li離子或Li S電池電極可由活性材料之漿料澆鑄混合物製成，該等活性材料包括以特定態樣比用於電池陰極中之諸如細碳黑及石墨之傳導性添加劑及經最佳化以產生由互連滲濾傳導性網狀結構界定之獨特自裝配形態之以聚合物為主之黏合劑。而在習知製備或應用中，添加劑及黏合劑可經最佳化以藉由例如提供較低界面阻抗來改進通過導電性且因此相對應地產生電力效能及輸送改進，其代表亦必須降低比(亦稱為重力)能量及密度，亦即當前要求高之高效能電池應用之不合需要最終結果的寄生塊體。The conventional composite material-type Li ion or Li S battery electrode can be made of a slurry casting mixture of active materials including conductive additives such as fine carbon black and graphite used in the battery cathode in a specific aspect ratio. The polymer-based adhesive is optimized to produce a unique self-assembled form defined by the interconnected percolation conductive network structure. In conventional preparations or applications, additives and adhesives can be optimized to improve conductivity by, for example, providing lower interfacial impedance, and therefore correspondingly generate power performance and improved delivery. The representative must also reduce the ratio. (Also known as gravity) energy and density, that is, the undesirable end result of the parasitic mass of the current demanding high-efficiency battery applications.

為最小化因寄生塊體所致之損失，諸如由經增大有效及/或無效比造成之損失，且同時使得電解質能夠較快到達電極之完整表面，擴散路徑109F可經再定向以有效縮短用於電荷轉移之Li離子擴散路徑長度。階層式孔隙101A及/或開放多孔支架102A可由尺寸縮小之碳粒子及/或降至奈米尺度之活性材料產生。定義為材料總表面積/單位質量(單位為m² /kg或m² /g)或固體或總體積(單位為m² /m³ 或m⁻¹ )之外比表面積(SSA)為可用於確定材料類型及特性之本發明所揭露之碳粒子中之任一個或多個的物理值。舉例而言，球體SSA隨直徑減小而增大。然而，當粒度下降至奈米尺寸範圍內時，存在可妨礙分散、促進黏聚且藉此增加電池阻抗且減弱電力效能之相關有吸引力凡得瓦爾力。In order to minimize the loss caused by the parasitic mass, such as the loss caused by the increased effective and/or ineffective ratio, and at the same time enable the electrolyte to reach the complete surface of the electrode faster, the diffusion path 109F can be redirected to effectively shorten Li ion diffusion path length for charge transfer. The hierarchical pores 101A and/or the open porous scaffold 102A can be produced by reduced-size carbon particles and/or active materials down to the nanometer scale. Defined as the total surface area of the material/unit mass (in m ² /kg or m ² /g) or solid or total volume (in m ² /m ³ or m ⁻¹ ), the specific surface area (SSA) can be used to determine The physical value of any one or more of the carbon particles disclosed in the present invention of the material type and characteristics. For example, the ball SSA increases as the diameter decreases. However, when the particle size falls within the nanometer size range, there are related attractive Van der Waals forces that can hinder dispersion, promote cohesion, and thereby increase battery impedance and weaken power performance.

用於縮短離子擴散路徑(指圖1F中所示之擴散路徑109F)之另一方法為獨特地工程改造構成性以碳為主之粒子，諸如由用於產生相連微結構107F之黏聚體101B產生之構成性以碳為主之粒子的內部孔隙度。表面曲率可稱為孔隙，此係在其空腔深度比寬度大之情況下如此。因此，此定義必須排除其中僅外表面積經修改之許多奈米結構碳材料，或其中諸如內部特定空間或區域之空隙係在鄰接粒子之間產生之經緊密封裝之粒子，如在習知漿料澆鑄電極之情況下一樣。Another method for shortening the ion diffusion path (referring to the diffusion path 109F shown in Figure 1F) is to uniquely engineer constituent carbon-based particles, such as the cohesive 101B used to create the connected microstructure 107F The internal porosity of the resulting constitutive particles is mainly carbon. The curvature of the surface can be referred to as a pore, which is the case when the depth of the cavity is greater than the width. Therefore, this definition must exclude many nano-structured carbon materials in which only the outer surface area is modified, or in which the voids such as specific internal spaces or regions are closely packed particles generated between adjacent particles, as in conventional slurries The same is true in the case of cast electrodes.

關於如先前實質上所描述指代在以微波為主之反應器中正在運行或在熱反應器中經由逐層沈積進行之以碳為主之粒子100A之合成、產生、形成及/或生長的工程改造，反應器過程參數可經調節以調諧以碳為主之粒子100A內階層式孔隙101A及/或相連微結構107F的尺寸、幾何結構以及分佈。以碳為主之粒子100A內階層式孔隙101A及/或相連微結構107F可經調適以達成特別充分地適合於諸如超電容器之高效能快速電流輸送裝置中之實施之效能圖。Regarding the synthesis, production, formation and/or growth of carbon-based particles 100A, which is essentially described previously, which is operating in a microwave-based reactor or through layer-by-layer deposition in a thermal reactor In engineering modification, the reactor process parameters can be adjusted to tune the size, geometry and distribution of the hierarchical pores 101A and/or the connected microstructures 107F in the carbon-based particles 100A. The hierarchical pores 101A and/or the connected microstructures 107F in the carbon-based particles 100A can be adapted to achieve a performance map that is particularly adequate for implementation in high-efficiency fast current delivery devices such as ultracapacitors.

如先前一般所描述，超電容器(supercapacitor，SC)亦稱為超電容器(ultracapacitor)，為電容值比其他電容器高得多、但電壓限值較低之橋接電解電容器與可充電電池之間之間隙的高容量電容器。其通常儲存比電解電容器多10至100倍之能量/單位體積或質量，可比電池快得多地接受且輸送電荷，且包容比可充電電池多得多之充電及放電循環。As previously described generally, supercapacitor (SC) is also called ultracapacitor, which is a bridge between electrolytic capacitor and rechargeable battery with much higher capacitance value than other capacitors but lower voltage limit. Of high-capacity capacitors. They usually store 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and transport charges much faster than batteries, and accommodate much more charge and discharge cycles than rechargeable batteries.

在於早期超電容器發展工作中使用之許多可獲得現成商業碳中，存在當在大電流密度及快速充電及放電速率下操作時變為瓶頸或不利條件之蠕蟲狀窄孔隙，此係因為電子可能會在該等結構或路徑中或周圍遇到流過困難。即使孔隙尺寸極其均一但仍可經調節以收納廣泛範圍之長度尺度，如基於蠕蟲狀窄孔隙所固有之結構挑戰，真實可達成之效能仍自我受限。In many of the available commercial carbons used in the early development of ultracapacitors, there are worm-like narrow pores that become bottlenecks or disadvantages when operating at high current densities and fast charging and discharging rates. This is due to the possibility of electrons. There will be difficulties in flow in or around such structures or paths. Even if the pore size is extremely uniform, it can still be adjusted to accommodate a wide range of length scales. For example, based on the inherent structural challenges of worm-like narrow pores, the actual achievable performance is still self-limited.

與具有經調諧至廣泛範圍之長度尺度之均一孔隙尺寸之習知多孔材料相比，本發明所揭露之3D階層式多孔材料，諸如由以碳為主之粒子100A內階層式孔隙101A及/或相連微結構107F顯示之3D階層式多孔材料可經合成以具有明確界定之孔隙尺寸，諸如相連微結構107F包括孔隙104F、105F及/或路徑106F及/或擴散路徑109F以及拓樸結構以藉由產生具有以下尺寸及/或寬度之多峰孔隙及/或通道來克服習知單一尺寸之多孔碳粒子的缺點： ●            中(2 nm ＜ d_孔隙 ＜ 50 nm)孔隙； ●            大(d_孔隙 ＞ 50 nm)孔隙201A，如圖2之顯微圖200中所示，以最小化質量運輸之擴散阻力；以及 ●            微(d_孔隙 ＜ 2 nm)孔隙202，以增大活性位點分散及/或離子儲存之表面積、與可儲存於給定孔隙尺寸，諸如由圖1F中之具有尺寸103F之孔隙105F顯示之孔隙尺寸內之離子密度及數目相關之電容。Compared with conventional porous materials with uniform pore sizes tuned to a wide range of length scales, the 3D hierarchical porous materials disclosed in the present invention, such as carbon-based particles 100A with internal hierarchical pores 101A and/or The 3D hierarchical porous material displayed by the connected microstructure 107F can be synthesized to have a well-defined pore size. For example, the connected microstructure 107F includes the pores 104F, 105F and/or the path 106F and/or the diffusion path 109F and the topological structure by Generate multimodal pores and/or channels with the following sizes and/or widths to overcome the shortcomings of conventional single-sized porous carbon particles: ● Medium (2 nm ＜ d _pore ＜50 nm) pores; ● Large (d _pore ＞50 nm) pore 201A, as shown in the micrograph 200 of Figure 2, to minimize the diffusion resistance of mass transport; and ● micro (d _pore <2 nm) pore 202 to increase active site dispersion and/or ion The stored surface area, and the capacitance that can be stored in a given pore size, such as the ion density and number within the pore size shown by the pore 105F with size 103F in FIG. 1F.

儘管尚未以實驗方式建立表面積與電容之間之簡單線性相關性，但以碳為主之粒子100A提供對於各預期最終用途應用及對應電壓窗口而言不同之最佳微孔尺寸分佈及/或組配。為使電容效能最佳化，以碳為主之粒子100A可合成有極窄孔隙尺寸分佈(PSD)；且當所需電壓升高時，較大孔隙為較佳的。無論如何，當前先進技術超電容器已提供用以工程改造本發明所揭露之3D階層式結構化材料以用於特定最終用途應用之路徑。Although the simple linear correlation between surface area and capacitance has not been established experimentally, the carbon-based particles 100A provide different optimal pore size distributions and/or groups for each expected end-use application and corresponding voltage window. match. In order to optimize the performance of the capacitor, the carbon-based particles 100A can be synthesized with extremely narrow pore size distribution (PSD); and when the required voltage increases, larger pores are preferred. In any case, the current advanced technology ultracapacitors have provided a path for engineering the 3D hierarchical structured materials disclosed in the present invention for specific end-use applications.

在超電容器中，電容及電力效能主要受例如以下控管： ●            孔隙壁之表面積； ●            孔隙尺寸；以及 ●            影響電雙層效能之孔隙通道之互連性。In ultracapacitors, capacitance and power performance are mainly controlled by, for example, the following: ● The surface area of the pore wall; ● Pore size; and ● The interconnectivity of pore channels that affect the performance of the electrical double layer.

相比之下，Li離子及/或Li-S儲存電池在活性材料內經歷法拉第(faradaic)還原/氧化反應且藉此可需要諸如有效地定向且/或縮短Li離子擴散路徑之超電容器之許多Li離子運輸部件。無論如何，在包括超電容器以及傳統Li離子或Li S二次電池之任何應用中，3D以奈米碳為主之構架/架構，諸如界定開放多孔支架102A之3D以奈米碳為主之構架/架構可諸如跨及沿石墨烯片之導電互連黏聚體101B、在例如具有高面積及體積比容量之高度負載活性材料旁邊提供連續電學傳導路徑。 用作用於陰極之形成材料之以碳為主之粒子 In contrast, Li-ion and/or Li-S storage batteries undergo a faradaic reduction/oxidation reaction within the active material and thereby may require many such as ultracapacitors that effectively orient and/or shorten the Li ion diffusion path Li ion transport parts. In any case, in any application including supercapacitors and traditional Li-ion or Li S secondary batteries, 3D nano-carbon-based frameworks/architectures, such as the 3D nano-carbon-based frameworks that define the open porous scaffold 102A The /architecture may provide a continuous electrical conduction path, such as the conductive interconnection cohesive 101B across and along the graphene sheet, next to a highly loaded active material having a high area and volume specific capacity, for example. Carbon-based particles used as the forming material for the cathode

為解決相對低電及離子傳導性、體積擴增以及當前Li S陰極電極設計中之聚硫化物(PS)溶解之盛行問題，以碳為主之粒子100A具有形成於其中以界定開放多孔支架102A之階層式孔隙101A及/或相連微結構107F，該開放多孔支架102A包括具有有適合於限制元素硫及/或Li S相關化合物之諸如約小於1.5 nm或1-4 nm空腔之尺寸103F之微孔結構的孔隙105F。開放多孔支架102A在限制硫時亦提供主體支架型結構以藉由例如反應器內經調適之碳(C)之原位氮(N)摻雜來管理S擴增，從而確保跨硫-碳(S-C)界面，諸如在孔隙105F內S及C之接觸及/或界面區域處之電子傳導。將S限制在奈米(nm)尺度空腔，諸如具有微孔織構103F之孔隙105F內有利地更改以下二者： ●            平衡飽和度，諸如溶解度乘積；以及 ●             S之結晶行為，以使得視在Li S化合物解離等時所需電學傳導可需要，在無控制不合需要之向陽極電極之PS遷移所需之外部動力情況下S保持被限制在具有尺寸103F之微孔織構或孔隙105F內。 因此，孔隙105F之尺寸103F引起不需要試圖妨礙聚硫化物(PS)擴散，同時負面地影響由歐姆(ohmic)阻力及電抗之組合作用以及極化引起之電池阻抗，諸如電路或組件對交流電之有效阻力的隔板。藉由使用具有相對於元素S、Li及/或Li S微米限制而言最佳及非最佳多峰孔隙分佈(指包括孔隙104F、102F及/或103F之相連微結構107F)或(可替代地)雙峰孔隙分佈之碳，以碳為主之粒子100A展現在經適當最佳化結構中之微米限制之操作原理。In order to solve the problem of relatively low electrical and ion conductivity, volume expansion, and the prevalence of polysulfide (PS) dissolution in the current LiS cathode electrode design, the carbon-based particles 100A have formed therein to define the open porous scaffold 102A The open-porous scaffold 102A includes a layered pore 101A and/or a connected microstructure 107F. The open porous scaffold 102A includes a cavity with a size 103F suitable for limiting element sulfur and/or Li S-related compounds, such as a cavity less than 1.5 nm or 1-4 nm. The pores of the microporous structure are 105F. The open porous scaffold 102A also provides a main scaffold structure when sulfur is restricted to manage S amplification by in-situ nitrogen (N) doping of carbon (C) adjusted for example in the reactor, thereby ensuring transsulfur-carbon (SC) ) Interface, such as the contact of S and C in the pore 105F and/or the conduction of electrons at the interface area. Restricting S to a nanometer (nm)-scale cavity, such as the pore 105F with a microporous texture 103F, advantageously modifies both of the following: ● Balance saturation, such as solubility product; and ● The crystallization behavior of S, so that electrical conduction may be required when the Li S compound is dissociated, etc., without the external power required to control the undesirable PS migration to the anode electrode, S remains limited to a size of 103F The microporous texture or pores within 105F. Therefore, the size 103F of the pore 105F does not need to try to hinder the diffusion of polysulfide (PS), and at the same time, it negatively affects the battery impedance caused by the combination of ohmic resistance and reactance and polarization, such as the resistance of the circuit or component to alternating current. A partition of effective resistance. By using an optimal and non-optimal multimodal pore distribution (referring to the connected microstructure 107F including pores 104F, 102F and/or 103F) or (alternatively Ground) The bimodal pore distribution of carbon, the carbon-based particle 100A exhibits the operating principle of micron limitation in a properly optimized structure.

該等經最佳化結構包括併有黏聚體101B，該等黏聚體101B自身可經製備以包括平行堆疊石墨烯層，諸如由具有強(002)維度之石墨至具有有低(002)維度之奈米觀孔隙之無規少層(FL)石墨烯產生之平行堆疊石墨烯層。圖1H及1I顯示定位於圖1H中個別石墨烯層電池及圖1I中在中間鄰接且平行石墨烯層內之碳晶格及結構中之Li離子之系統間夾。示於圖1I中之組配可包括多個階段，包括階段1至3，各狀態表示各種尺寸及間距位準之石墨層平面，以在陰極處產生約372 mAh/g或更大之理論比容量。The optimized structures include cohesive 101B, which can be prepared by themselves to include parallel stacked graphene layers, such as graphite with strong (002) dimensions to low (002) Dimensional nano-porosity random few-layer (FL) graphene produces parallel stacked graphene layers. Figures 1H and 1I show the intercalation of Li ions in the carbon lattice and structure located in the individual graphene layer cells in Figure 1H and in the adjacent and parallel graphene layers in Figure 1I. The assembly shown in Figure 1I can include multiple stages, including stages 1 to 3. Each state represents a graphite layer plane of various sizes and spacing levels to produce a theoretical ratio of about 372 mAh/g or greater at the cathode. capacity.

圖2顯示超過圖1I中階段1至3中所示之習知鄰接堆疊FL石墨烯層之進化，其中形成深度延伸至若干鄰接堆疊FL石墨烯層中之空腔，各層具有介於約3.34 Å至4.0 Å或3 Å至20 Å範圍內之可調諧D-間距。因此，Li離子可間夾在鄰接石墨烯層之間以及在亦稱為奈米觀孔隙之空腔之暴露表面上形成層，以產生超過750 mAh/g之比容量範圍。根據一些實施方案，當共同觀測時，3D自裝配無黏合劑以碳為主之粒子之例示性經放大部分可聚結以形成可包括圖1A至圖1F中所示之本發明所揭露之以碳為主之結構中之任一個或多個的以碳為主之網狀結構、晶格、支架或粒子。以碳為主之網狀結構可包括多個大孔隙或微孔隙202中之任一個或多個。Figure 2 shows an evolution beyond the conventional adjacent stacked FL graphene layers shown in Figure 1I in stages 1 to 3, in which cavities are formed that extend to a depth of several adjacent stacked FL graphene layers, and each layer has a value between about 3.34 Å Tunable D-spacing in the range of 4.0 Å or 3 Å to 20 Å. Therefore, Li ions can be sandwiched between adjacent graphene layers and form a layer on the exposed surface of the cavity, also called nanopore, to produce a specific capacity range exceeding 750 mAh/g. According to some embodiments, when viewed together, an exemplary enlarged portion of the 3D self-assembled binder-free carbon-based particles may coalesce to form the components disclosed in the present invention as shown in FIGS. 1A to 1F. Any one or more of carbon-based network structures, lattices, scaffolds, or particles. The carbon-based network structure may include any one or more of a plurality of macropores or micropores 202.

以碳為主之粒子100A亦提供使圖3中所示之碳支架300有效地負載或灌注有元素Li，諸如由熔融Li金屬或其蒸氣衍生物提供之元素Li之能力。碳支架300可藉由以下在反應器中產生： ●             藉由漿料情況方法逐層沈積多個以碳為主之粒子100A；或 ●            如由圖4B)中之電漿噴射炬系統400B所示，藉由具有諸如元素硫之硫之連續順序之一組電漿噴射炬。The carbon-based particles 100A also provide the ability to effectively load or impregnate the carbon scaffold 300 shown in FIG. 3 with elemental Li, such as element Li provided by molten Li metal or its vapor derivative. The carbon support 300 can be produced in the reactor by: ● Deposit multiple carbon-based particles 100A layer by layer by means of slurry conditions; or ● As shown by the plasma jet torch system 400B in FIG. 4B), by a series of plasma jet torches having a continuous sequence of sulfur such as elemental sulfur.

對於可靠地超過習知Li離子電池之Li S電池效能，工業可升級技術必須達成相對於給定陰極模板之全部添加劑及組分而言高S負載量，諸如＞ 70%硫/單位體積，同時維持S活性材料之天然比容量。諸如藉由獨立地或以任何組合形式執行之電解、濕式化學、簡單混合、球磨碾磨、噴塗以及陰極電解質中之任一者或多者將S併入陰極主體中之嘗試已按需要不完全併有S或在其他方面在經濟上不可升級或不可製造。For Li S battery performance that reliably exceeds conventional Li-ion batteries, industrial scalable technology must achieve high S loading relative to all additives and components of a given cathode template, such as> 70% sulfur per unit volume, while Maintain the natural specific capacity of S active material. Attempts to incorporate S into the cathode body by any one or more of electrolysis, wet chemistry, simple mixing, ball milling, spraying, and catholyte performed independently or in any combination have not been as necessary. Completely incorporated S or otherwise not economically upgradeable or non-manufacturable.

與其中小孔隙熱力學上不能達到之熔融浸潤不同，本發明所揭露之合成方法可使用在實質上大氣壓下引入且反應之等溫蒸氣技術，其中奈米尺度孔隙或表面之高表面自由能驅動含硫液體之自發性成核直至含硫及/或鋰縮合物之保形塗層到達階層式孔隙101A及/或相連微結構107F之內向表面上為止。本質上，獨特蒸氣灌注方法將硫灌注至細孔隙中，該等細孔隙諸如為以碳為主之粒子100A之核處之階層式孔隙101A及/或相連微結構107F及/或孔隙104F、105F及/或路徑106F及/或擴散路徑109F中之任一者或多者，且因此不僅在其表面處。 用於產生導電支架之以碳為主之粒子 Different from the melting and infiltration of small pores which cannot be achieved thermodynamically, the synthesis method disclosed in the present invention can use isothermal vapor technology introduced and reacted under substantially atmospheric pressure, in which nano-scale pores or high surface free energy on the surface drive sulfur content. The liquid spontaneously nucleates until the conformal coating containing sulfur and/or lithium condensate reaches the inner surface of the hierarchical pore 101A and/or the connected microstructure 107F. Essentially, the unique vapor injection method injects sulfur into fine pores, such as the hierarchical pore 101A and/or the connected microstructure 107F and/or the pores 104F, 105F at the core of the carbon-based particle 100A And/or any one or more of the path 106F and/or the diffusion path 109F, and therefore not only at its surface. Carbon-based particles used to produce conductive scaffolds

以碳為主之粒子100A可使用已知技術及本文所揭露之新穎技術以任何數目之方式製造，該等技術包括： ●            漿料澆鑄，指代其中通常將液體材料傾入含有具有所需形狀之中空空腔之模具中且隨後使其凝固之習知金屬加工、製造及/或製造技術；或 ●            電漿噴射炬系統400B，諸如圖4B中所示之電漿噴射炬系統400B，其可用於執行逐層沈積以逐漸地生長以碳為主之粒子100A。The carbon-based particles 100A can be manufactured in any number of ways using known technologies and the novel technologies disclosed herein, including: ● Slurry casting refers to conventional metal processing, manufacturing and/or manufacturing techniques in which liquid materials are usually poured into a mold containing a hollow cavity with a desired shape and then solidified; or The plasma jet torch system 400B, such as the plasma jet torch system 400B shown in FIG. 4B, can be used to perform layer-by-layer deposition to gradually grow carbon-based particles 100A.

如上文所描述之任一技術或任何其他已知或新穎製造技術可用於以分級方式產生圖3中所示之碳支架300。如由描述如下之電學梯度及離子傳導梯度中之任一者或多者至少部分指定，對電學梯度之控制可產生具有變化導電性度之碳支架300： ●            電學梯度可由實質上正交熔合在一起以形成開放多孔支架102A之石墨烯片101B界定，其中電學傳導沿及跨石墨烯片101B之接觸點發生；且 ●            諸如通過階層式孔隙101A及相連微結構107F之Li離子運輸、移動或遷移之離子傳導梯度可在以碳為主之粒子100之某些組配中受益於如圖3B中所示在豎直高度方向A在整個厚度之碳支架300B中之擴散路徑109F之有效縮短，該有效縮短用以例如准許間夾在諸如石墨烯片101B之鄰接少層石墨烯片之間之Li離子朝向碳支架300B周圍之液體電解質在途逸出且遷移至陰極固化電化電池放電-充電循環。Any of the techniques described above or any other known or novel manufacturing techniques can be used to produce the carbon scaffold 300 shown in FIG. 3 in a hierarchical manner. As specified at least in part by any one or more of an electrical gradient and an ion conduction gradient as described below, the control of the electrical gradient can produce a carbon scaffold 300 with varying degrees of conductivity: ● The electrical gradient can be defined by the graphene sheets 101B that are fused together substantially orthogonally to form the open porous scaffold 102A, where the electrical conduction occurs along the contact points across the graphene sheet 101B; and ● Ion conduction gradients such as Li ion transport, movement or migration through the hierarchical pore 101A and the connected microstructure 107F can benefit from the vertical The effective shortening of the diffusion path 109F in the height direction A in the entire thickness of the carbon support 300B is used, for example, to allow Li ions sandwiched between adjacent few-layer graphene sheets such as the graphene sheet 101B to face the carbon support 300B The surrounding liquid electrolyte escapes and migrates to the discharge-charge cycle of the cathode-cured electrochemical cell.

在整個本發明所揭露之實施方案中，已提及在反應器內正在運行地合成以產生石墨烯片101B之碳之各種形式，該等石墨烯片101B經互連且沿接觸點傳導電且可發生形狀、尺寸、位置、定向及/或結構變化。該等變化可在結晶度差異及用於產生石墨烯片之導電互連黏聚體101B之特定類型之一或多個碳同素異形體方面受影響。結晶度意指固體中結構等級度。在晶體中，原子或分子以規則週期性方式佈置。因此，結晶度對硬度、密度、透明度以及擴散具有相當大影響。Throughout the disclosed embodiments of the present invention, various forms of carbon that are operatively synthesized in a reactor to produce graphene sheets 101B have been mentioned. The graphene sheets 101B are interconnected and conduct electricity along the contact points. Changes in shape, size, position, orientation, and/or structure can occur. These changes can be affected in terms of differences in crystallinity and specific types of one or more carbon allotropes of the conductive interconnected cohesive 101B used to produce graphene sheets. Crystallinity means the degree of structure in a solid. In crystals, atoms or molecules are arranged in a regular periodic manner. Therefore, crystallinity has a considerable influence on hardness, density, transparency and diffusion.

因此，以碳為主之粒子100可以諸如以碳為主之支架之經組織支架形式在反應器外產生或在反應器內之主要合成之外發生之後處理活動期間產生。Therefore, the carbon-based particles 100 may be produced outside the reactor in the form of a tissue-based scaffold such as a carbon-based scaffold or during processing activities after the main synthesis takes place outside the reactor.

如2017年9月19日發佈之Stowell等人, 「Microwave Chemical Processing Reactor」，美國專利第9,767,992號所揭露，電漿處理及/或以電漿為主之處理可在反應器內進行，其中供應氣體係用於在電漿區中生成電漿以在反應區中將諸如甲烷及/或其他合適於氣相中之烴之過程輸入材料轉化成經分離組分，從而促進以碳為主之材料之正在運行之合成。As disclosed by Stowell et al., "Microwave Chemical Processing Reactor", US Patent No. 9,767,992 published on September 19, 2017, plasma processing and/or plasma-based processing can be performed in a reactor, where the supply The gas system is used to generate plasma in the plasma zone to convert process input materials such as methane and/or other hydrocarbons suitable for the gas phase into separated components in the reaction zone, thereby promoting carbon-based materials The running synthesis.

作為藉由如上文所描述之微波反應器或在其內進行之合成之替代方案，熱能可朝向或接近於氣相中供應之含碳原料材料被導引至圖3中所示之碳支架300之犧牲基體306上以藉由例如圖4B中所示之電漿噴射炬系統400B依序沈積多層以碳為主之粒子100A。該等粒子可在微波反應器中正在運行地熔合在一起或在熱反應器中以受控方式沈積以達成以碳為主之粒子100A之變化濃度位準，因此之後達成與碳支架300中以碳為主之粒子100A之濃度位準成比例之分級導電性。該等程序可用於調配諸如在導電性及離子運輸方面具有高度可調諧性之諸如碳支架300之多孔以碳為主之電極結構，同時亦消除許多產生步驟且以其他方式保留習知外部外觀。As an alternative to the synthesis by or within the microwave reactor as described above, the heat energy can be directed towards or close to the carbon-containing feedstock material supplied in the gas phase to the carbon support 300 shown in FIG. 3 On the sacrificial substrate 306, for example, the plasma spray torch system 400B shown in FIG. 4B is used to sequentially deposit multiple layers of carbon-based particles 100A. The particles can be fused together in operation in a microwave reactor or deposited in a controlled manner in a thermal reactor to achieve a varying concentration level of the carbon-based particles 100A, so that they can later be combined with the carbon support 300 The graded conductivity of the carbon-based particles 100A is proportional to the concentration level. These procedures can be used to prepare a porous carbon-based electrode structure such as the carbon scaffold 300, which is highly tunable in terms of conductivity and ion transport, while also eliminating many production steps and retaining the conventional external appearance in other ways.

可產生具有開放蜂窩狀結構之開放多孔支架102A以使得液相電解質可易於浸潤至於其中之各種孔隙中，該等孔隙諸如為相連微結構107F之路徑、空隙及其類似者中之任一個或多個。開放多孔支架102A之框架部分可稱為基底或構架，且諸如階層式孔隙101A及/或相連微結構107F之孔隙可浸潤有流體、液體或氣體，而框架材料通常成型為固體材料。 以碳為主之粒子之孔隙度 The open porous scaffold 102A having an open honeycomb structure can be produced so that the liquid electrolyte can easily infiltrate into various pores therein, such as any one or more of the paths connecting the microstructure 107F, the voids, and the like. Piece. The frame portion of the open porous scaffold 102A can be called a substrate or a framework, and the pores such as the hierarchical pores 101A and/or the connected microstructures 107F can be infiltrated with fluid, liquid or gas, and the frame material is usually formed as a solid material. Porosity of carbon-based particles

諸如以碳為主之粒子100A之多孔介質之特徵可在於其孔隙度。諸如滲透性、抗拉強度、導電性以及扭曲度之介質其他特性可衍生自其組分、散佈於其中之固體基質及流體以及介質孔隙度及孔隙結構之相應特性。具有貫穿其中散佈之相連微結構107F之以碳為主之粒子100A可在反應器外產生以達成有助於Li離子擴散之所需孔隙度位準。與該Li離子擴散相關，石墨烯片101B促進沿其接觸點之電子傳導，同時亦允許電子在反應位點處與正Li離子再聯合。A porous medium such as carbon-based particles 100A may be characterized by its porosity. Other properties of the medium, such as permeability, tensile strength, conductivity, and degree of torsion, can be derived from its composition, the solid matrix and fluid dispersed in it, and the corresponding properties of the porosity and pore structure of the medium. Carbon-based particles 100A with connected microstructures 107F dispersed throughout can be produced outside the reactor to achieve the desired porosity level that facilitates the diffusion of Li ions. In connection with the diffusion of Li ions, the graphene sheet 101B promotes the conduction of electrons along its contact points, while also allowing electrons to recombine with positive Li ions at the reaction sites.

關於以碳為主之粒子100A之開放多孔支架102A之孔隙度及扭曲度，可在玻璃瓶中製造大理石類似物。在此實例中，孔隙度係指允許液相電解質滲入類似於界定以碳為主之粒子100A內擴散路徑109F之相連微結構107F的大理石之間之空隙空間中的大理石之間之間距。大理石自身可藉由允許電解質不僅滲於石墨烯片101B之間之裂縫中且亦滲於各石墨烯片自身中而類似於瑞士乳酪，個別石墨烯片示於圖1C中。在此實例以及其他實例中，擴散路徑109F之相對縮短係指Li離子藉由例如毛細管作用浸潤於其中以接觸諸如被限制於孔隙105F內之S之活性材料所花費的時間。擴散路徑109F適應可含有Li離子之電解質向以碳為主之粒子100A中之便利且快速浸潤及擴散，該以碳為主之粒子100A隨後可生長或以其他方式進一步合成以產生具有分級導電性之碳支架300。Regarding the porosity and distortion of the open porous scaffold 102A of the carbon-based particles 100A, a marble analog can be manufactured in a glass bottle. In this example, the porosity refers to the distance between marbles in the void space between the marbles that allow the liquid electrolyte to penetrate into the interstitial spaces similar to the connected microstructures 107F in the diffusion path 109F of the carbon-based particles 100A. The marble itself can be similar to Swiss cheese by allowing the electrolyte to not only penetrate the cracks between the graphene sheets 101B but also into the respective graphene sheets themselves. The individual graphene sheets are shown in FIG. 1C. In this example and other examples, the relative shortening of the diffusion path 109F refers to the time it takes for Li ions to infiltrate it by capillary action to contact the active material such as S confined in the pore 105F. The diffusion path 109F adapts to the convenient and rapid infiltration and diffusion of the electrolyte containing Li ions into the carbon-based particles 100A. The carbon-based particles 100A can then be grown or further synthesized in other ways to produce graded conductivity The carbon bracket 300.

擴散路徑109F之縮短係指在碳支架300中之開放多孔支架102A內Li離子通過其移動且不具有自身被限制於相連微結構107F之孔隙105F內之諸如S之活性材料的擴散長度縮短。此與需要僅藉由使活性材料厚度較小(lesser/smaller)來縮短活性材料之擴散長度之習知技術形成對比。相連微結構107F內之擴散路徑109F可藉由控制於其中之Li離子流動及/或運輸而充當Li離子緩衝儲集器以為如可有益於Li離子限制、如與孔隙105之經S塗佈之暴露碳表面反應的於其中之Li離子運輸及稍後電化電池充電-放電循環期間之Li離子運輸提供更自由的流動結構。Li離子在圖1F中所示之一般方向遍及擴散路徑109F之運輸可發生在最初被灌注且在開放多孔支架102A內捕獲之液體電解質中，其中該電解質灌注發生在於放電-充電循環中使用環狀碳支架300之前。The shortening of the diffusion path 109F refers to the shortening of the diffusion length of the active material such as S in the open porous scaffold 102A in the carbon scaffold 300 through which Li ions move without being confined in the pores 105F of the connected microstructure 107F. This is in contrast to the conventional technology that requires only the lesser/smaller thickness of the active material to shorten the diffusion length of the active material. The diffusion path 109F in the connected microstructure 107F can act as a Li ion buffer reservoir by controlling the flow and/or transportation of Li ions therein, as it can be beneficial for Li ion confinement, such as the S-coated with the pore 105 The Li ion transport in which the exposed carbon surface reacts and later during the charge-discharge cycle of the electrochemical cell provides a more free flowing structure. The transport of Li ions throughout the diffusion path 109F in the general direction shown in FIG. 1F can occur in the liquid electrolyte that is initially perfused and captured in the open porous stent 102A, where the electrolyte perfusion occurs in the discharge-charge cycle using a ring Before the carbon bracket 300.

存在以下實例：准許液相電解質在以碳為主之粒子100A之開放多孔支架102A中之最初擴散及分佈以填充且佔據階層式孔隙101A及/或相連微結構107F，之後使用藉由逐層沈積以碳為主之粒子100A合成或以其他方式產生之碳支架300。真空或空氣亦可用於填充階層式孔隙101A及/或相連微結構107F，此舉可允許或輔助開放多孔支架102A內含碳暴露表面之電解質潤濕。There are the following examples: allow the initial diffusion and distribution of the liquid electrolyte in the open porous scaffold 102A of the carbon-based particles 100A to fill and occupy the hierarchical pores 101A and/or the connected microstructure 107F, and then use by layer-by-layer deposition A carbon scaffold 300 made of carbon-based particles 100A synthesized or produced in other ways. Vacuum or air can also be used to fill the hierarchical pores 101A and/or the connected microstructures 107F, which can allow or assist the electrolyte wetting of the carbon-containing exposed surface of the open porous scaffold 102A.

Li離子藉由鏈反應自一個位置彈跳至另一位置，此類似於牛頓球撞擊，在該牛頓球撞擊中一個球擊中以引起力轉移，從而引起其他球移動。類似地，各Li離子移動相對短距離，但保持能夠經由如所描述之此類型之鏈反應集體移動大量Li離子。如可為Li離子及/或粒子在石墨烯片之黏聚體101B中、周圍或內之結晶佈置，個別Li離子移動程度可受經由毛細管灌注至開放多孔支架102A中而向碳支架300B一起供應之Li離子之數量影響。 由碳支架產生之電化電池陽極或陰極 Li ions bounce from one position to another through a chain reaction, which is similar to a Newton ball impact, in which a ball hits to cause a force transfer, which causes other balls to move. Similarly, each Li ion moves a relatively short distance, but remains able to collectively move a large number of Li ions via this type of chain reaction as described. For example, it can be the crystalline arrangement of Li ions and/or particles in, around, or in the cohesive body 101B of the graphene sheet, the mobility of individual Li ions can be injected into the open porous stent 102A through the capillary tube and supplied to the carbon stent 300B. The amount of Li ions. Electrochemical battery anode or cathode produced by carbon stent

圖3中所示之碳支架300可整合於電池或超電容器應用、包括Li離子電池及Li S電池之電池類型中。碳支架300可被併入陽極或陰極中以用於Li離子及Li S電池系統，但需要製備相連微結構107F以將S限制在孔隙105F或其他地方中以適應聚硫化物(PS)之產生及限制以及PS遷移之控制。例示性電池系統可包括經組配以向系統供應電力之電化電池。電化電池可具有含有陽極活性材料之陽極、含有陰極活性材料之陰極、安置於陽極與陰極之間之多孔隔板以及與陽極活性材料及陰極活性材料離子接觸之電解質。The carbon support 300 shown in FIG. 3 can be integrated in battery or supercapacitor applications, including Li-ion batteries and Li S batteries. The carbon support 300 can be incorporated into the anode or cathode for use in Li ion and Li S battery systems, but the connected microstructure 107F needs to be prepared to confine S in the pore 105F or other places to accommodate the production of polysulfide (PS) And restrictions and control of PS migration. An exemplary battery system may include electrochemical batteries configured to supply power to the system. An electrochemical cell may have an anode containing an anode active material, a cathode containing a cathode active material, a porous separator disposed between the anode and the cathode, and an electrolyte in ionic contact with the anode active material and the cathode active material.

陽極及陰極可包括導電之犧牲基體306，其中當第一相連膜具有第一濃度之以碳為主之粒子100A時，第一層沈積於其上，該等以碳為主之粒子100A在圖3中顯示為以碳為主之粒子302以使得省去其之冗餘描述。The anode and the cathode may include a conductive sacrificial substrate 306, wherein when the first connected film has a first concentration of carbon-based particles 100A, the first layer is deposited on it. The carbon-based particles 100A are shown in the figure. 3 is shown as a carbon-based particle 302 so that redundant descriptions are omitted.

多孔配置形成於如由以碳為主之粒子302界定之碳支架300中，該等以碳為主之粒子302與鄰接在一起之多個以碳為主之粒子100A同義且可與其互換使用，且較小碳粒子304遍及碳支架300散佈。碳支架300之多孔配置接納分散於其中之電解質以用於通過與個別以碳為主之粒子100A及/或302類似界定一或多個通道之互連階層式孔隙101A及/或相連微結構107F的Li離子運輸，該一或多個通道包括： ●            提供可調諧Li離子管道之由＞ 50 nm之尺寸101F界定之微孔構架； ●            充當於其中之用於快速Li離子運輸之Li離子高速通道之由約20 nm至約50 nm之尺寸101F界定(一般根據IUPAC命名法界定且稱為中孔或中孔的)之中孔通道；以及 ●            用於電荷收納及/或活性材料限制之由＜ 4 nm之尺寸103F界定之微孔織構。The porous configuration is formed in the carbon scaffold 300 as defined by carbon-based particles 302. The carbon-based particles 302 are synonymous with and can be used interchangeably with a plurality of adjacent carbon-based particles 100A. And the smaller carbon particles 304 are scattered throughout the carbon support 300. The porous configuration of the carbon scaffold 300 accepts electrolyte dispersed therein for the purpose of defining one or more channels of interconnected hierarchical pores 101A and/or connected microstructures 107F by similarly to individual carbon-based particles 100A and/or 302 For Li ion transport, the one or more channels include: ● Provide a tunable Li ion pipe with a microporous framework defined by 101F with a size> 50 nm; ● Mesoporous channels defined by 101F (generally defined according to IUPAC nomenclature and called mesopores or mesopores) with a size of 101F from about 20 nm to about 50 nm serving as the Li ion high-speed channel for rapid Li ion transport ;as well as ● A microporous texture defined by a size of 103F <4 nm for charge storage and/or active material restriction.

包括第一濃度之以碳為主之粒子100A及/或302之第一層可經組配以展現介於500 S/m至20,000 S/m範圍內之導電性。第二層或任何後一層可沈積於第一層或任何前一層上。第二層可包括藉由第二濃度之彼此接觸之以碳為主之粒子100A及/或302形成之第二相連膜以產生介於0 S/m至500 S/m範圍內或在其他方面低於第一導電性之第二導電性。The first layer including the first concentration of carbon-based particles 100A and/or 302 may be configured to exhibit conductivity in the range of 500 S/m to 20,000 S/m. The second layer or any subsequent layer can be deposited on the first layer or any previous layer. The second layer may include a second connected film formed by carbon-based particles 100A and/or 302 that are in contact with each other at a second concentration to produce a range of 0 S/m to 500 S/m or in other aspects A second conductivity lower than the first conductivity.

碳支架300可經製備以用於在本文中稱為預鋰化之後續Li浸潤，且稍後經由毛細管作用灌注有Li離子液體溶液以產生如圖4A中所示之鋰化碳支架400A。各自在自集電器延伸之豎直方向具有經界定厚度之膜層406A、408A、410A以及412A可在微波反應器中正在運行地合成或在熱反應器中或外逐層沈積。膜層406A、408A、410A以及412A在與集電器正交之方向且遠離集電器具有介於諸如在膜層406A處高至諸如在膜層412A處低範圍內之變化導電性，該集電器亦可為犧牲及/或導電基體。在一例示性組配中，可產生具有經界定且逐漸降低之濃度的以碳為主之粒子302的膜層406A、408A、410A以及412A之各層，以達成特定電阻值，諸如在以下情況下： ●            產生具有相對高經界定濃度的以碳為主之粒子302的膜層406A，該相對高經界定濃度之以碳為主之粒子302有助於低Li離子運輸及＜ 1,000 Ω之低電阻，適用於高導電性； ●            產生具有系統地降低之導電性的膜層408A及410A，其係藉由工程改造以碳為主之粒子302以展現所需界面表面張力來促進暴露碳表面之熔融Li金屬潤濕；以及 ●            產生具有相對低經界定濃度的以碳為主之粒子302的膜層412A，該相對低經界定濃度之以碳為主之粒子302有助於高Li離子運輸及＞ 1,000-10,000 Ω之高電阻，適用於高電阻。The carbon scaffold 300 may be prepared for subsequent Li infiltration referred to herein as prelithiation, and later infused with a Li ionic liquid solution via capillary action to produce a lithiated carbon scaffold 400A as shown in FIG. 4A. The film layers 406A, 408A, 410A, and 412A, each having a defined thickness in the vertical direction extending from the current collector, can be synthesized in operation in a microwave reactor or deposited layer by layer in or outside of a thermal reactor. The film layers 406A, 408A, 410A, and 412A in the direction orthogonal to the current collector and away from the current collector have varying electrical conductivity ranging from as high as at the film layer 406A to as low as at the film layer 412A, and the current collector also It can be a sacrificial and/or conductive substrate. In an exemplary configuration, each layer of film layers 406A, 408A, 410A, and 412A with a defined and gradually decreasing concentration of carbon-based particles 302 can be produced to achieve a specific resistance value, such as in the following cases : ● Produce a film 406A with a relatively high defined concentration of carbon-based particles 302. The relatively high defined concentration of carbon-based particles 302 contributes to low Li ion transport and low resistance <1,000 Ω. Suitable for high conductivity; ● Produce films 408A and 410A with systematically reduced conductivity, which are engineered by carbon-based particles 302 to exhibit the required interfacial surface tension to promote the wetting of molten Li metal on the exposed carbon surface; and ● Produce a film layer 412A with a relatively low defined concentration of carbon-based particles 302, the relatively low defined concentration of carbon-based particles 302 contributes to high Li ion transport and higher than 1,000-10,000 Ω Resistance, suitable for high resistance.

變化導電性可與被浸潤至開放多孔支架之多孔配置中之Li離子溶液之界面表面張力至少部分成比例。Li離子溶液浸潤可經由經工程改造以促進暴露於Li離子溶液之開放多孔支架102A之表面潤濕之毛細管灌注來執行。如圖1F中所示之擴散路徑109F確保與發生在以碳為主之粒子100A及/或302B內之一或多個氧化還原(oxidation-reduction) (亦稱為氧化還原(redox))反應相關聯之沈積及剝離操作為均一的。電活性材料可在其用於形成開放多孔支架102A時駐存於相連微結構107F之孔隙105F中，該開放多孔支架102A自身可併於陽極及陰極中之任一者或多者內。在一些實施方案中，相連微結構107F可由以下形成或以其他方式含有以下：如圖1C中所示之單層石墨烯(SLG)及/或顯示為圖1B中多層石墨烯片101C之黏聚體101B之包括1至10個石墨烯平面之少層石墨烯(FLG)。石墨烯片101C群組可以實質上對準定向沿豎軸定位且以實質上正交角度熔合在一起。陽極活性材料或陰極活性材料可在以乾燥狀態量測時具有約500 m² /g至2,675 m² /g之比表面積，且可含有適用於鋰化之石墨烯材料，該石墨烯材料包含以下中之任一者或多者：預鋰化石墨烯片、初始石墨烯、氧化石墨烯、還原氧化石墨烯、氟化石墨烯、氯化石墨烯、溴化石墨烯、碘化石墨烯、氫化石墨烯、氮化石墨烯、硼摻雜石墨烯、氮摻雜石墨烯、化學官能化石墨烯、其物理或化學活化或蝕刻型式、其傳導性聚合物塗佈或接枝型式及/或其組合。The varying conductivity can be at least partially proportional to the interfacial surface tension of the Li ion solution infiltrated into the porous configuration of the open porous scaffold. Li ion solution infiltration can be performed via capillary perfusion engineered to promote wetting of the surface of the open porous stent 102A exposed to the Li ion solution. The diffusion path 109F as shown in Figure 1F ensures that it is related to one or more oxidation-reduction (also known as redox) reactions occurring in the carbon-based particles 100A and/or 302B The deposition and stripping operations of the strip are uniform. The electroactive material can reside in the pores 105F of the connected microstructure 107F when it is used to form the open porous scaffold 102A, which itself can be incorporated in any one or more of the anode and the cathode. In some embodiments, the connected microstructures 107F may be formed by or otherwise contain the following: single-layer graphene (SLG) as shown in FIG. 1C and/or as shown in FIG. 1B as the cohesion of the multilayer graphene sheet 101C The body 101B includes 1 to 10 graphene plane few-layer graphene (FLG). The group of graphene sheets 101C can be positioned along a vertical axis in a substantially aligned orientation and fused together at a substantially orthogonal angle. The anode active material or the cathode active material may have a ^{specific surface area of about 500 m 2} /g to 2,675 m ² /g when measured in a dry state, and may contain graphene materials suitable for lithiation. The graphene materials include the following Any one or more of: pre-lithiated graphene sheets, initial graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated Graphene, graphene nitride, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, its physically or chemically activated or etched type, its conductive polymer coating or grafting type, and/or its combination.

在與鋰化碳支架400A相關之所論述實例中之任一個或多個中，石墨烯片之導電互連黏聚體101B燒結在一起以不依賴於黏合劑形成開放多孔支架，然而，存在其中使用黏合劑之替代性實例。利用或不利用黏合劑之組配可各自涉及充當(act as/serve as)比容量為約744 - 1,116 mAh/g或更大之活性鋰間夾結構之開放多孔支架102A。此外，實例包括使用化學官能化石墨烯進行之石墨烯片101B製備，該製備涉及其表面官能化，包含向開放多孔支架102A賦予選自醌、氫醌、四級銨化芳胺、硫醇、二硫化物、磺酸酯(- SO₃ )、過渡金屬氧化物、過渡金屬硫化物、其他類似化合物或其組合之官能基。In any one or more of the discussed examples related to the lithiated carbon scaffold 400A, the conductive interconnected aggregates 101B of the graphene sheets are sintered together to form an open porous scaffold without relying on adhesives, however, there are Alternative examples of using adhesives. The combination with or without the adhesive may each involve acting as/serve as an open porous scaffold 102A of an active lithium sandwich structure with a specific capacity of about 744-1,116 mAh/g or greater. In addition, examples include the preparation of graphene sheet 101B using chemically functionalized graphene, which involves surface functionalization, including imparting to the open porous scaffold 102A selected from quinones, hydroquinones, quaternary ammonium arylamines, thiols, Functional groups of disulfide, sulfonate (-SO ₃ ), transition metal oxide, transition metal sulfide, other similar compounds, or combinations thereof.

圖4A中所示之集電器為例如至少部分地以發泡體為主或衍生於發泡體且可選自以下中之任一者或多者：金屬發泡體、金屬網、金屬篩網、穿孔金屬、以片材為主之3D結構、金屬纖維墊、金屬奈米線墊、傳導性聚合物奈米纖維墊、傳導性聚合物發泡體、傳導性聚合物塗佈纖維發泡體、碳發泡體、石墨發泡體、碳氣凝膠、碳乾凝膠、石墨烯發泡體、氧化石墨烯發泡體、還原氧化石墨烯發泡體、碳纖維發泡體、石墨纖維發泡體、剝離型石墨發泡體及其組合。The current collector shown in FIG. 4A is, for example, at least partially based on or derived from foam and can be selected from any one or more of the following: metal foam, metal mesh, metal mesh , Perforated metal, sheet-based 3D structure, metal fiber mat, metal nanowire mat, conductive polymer nanofiber mat, conductive polymer foam, conductive polymer coated fiber foam , Carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber hair Foam, exfoliated graphite foam and combinations thereof.

在本文中稱為活性材料之陽極或陰極導電或絕緣材料可包括選自以下之無機材料之奈米盤、奈米薄片、奈米富勒烯、碳奈米洋蔥(CNOs)、奈米塗料或奈米片中之任一者或多者： ●            硒化鉍或碲化鉍， ●            過渡金屬二硫屬化物或三硫屬化物， ●            過渡金屬硫化物、硒化物或碲化物； ●            氮化硼或 ●            其組合，包括散佈於其中之熔融Li金屬以在正常電化電池放電-電荷循環期間解離時提供Li離子源等。 奈米盤、奈米薄片、奈米塗料或奈米片之厚度可小於100 nm。在其他實例中，奈米薄片之厚度可小於10 nm且/或長度、寬度或直徑可小於5 µm。 產生由碳結構產生之陽極或陰極 The anode or cathode conductive or insulating material referred to herein as the active material may include nanodisks, nanosheets, nanofullerenes, carbon nano onions (CNOs), nano coatings or inorganic materials selected from the group below Any one or more of the nanosheets: ● bismuth selenide or bismuth telluride, ● transition metal dichalcogenides or trichalcogenides, ● transition metal sulfides, selenides or tellurides; ● boron nitride Or ● The combination includes molten Li metal dispersed therein to provide a Li ion source when dissociated during normal electrochemical cell discharge-charge cycles, etc. The thickness of nanoplates, nanosheets, nano coatings or nanosheets can be less than 100 nm. In other examples, the thickness of the nanoflake can be less than 10 nm and/or the length, width, or diameter can be less than 5 µm. Produce anode or cathode produced by carbon structure

用於產生三維(3D)以碳為主之電極，諸如由鋰化碳支架400A產生之電極之例示性方法可包括諸如由其中熱能係傳送通過電漿及/或以氣態供應之原料材料之一或多個以電漿為主之熱反應器或炬沈積以碳為主之粒子100A或400A來在基體上形成第一相連膜層，諸如圖4A中所示之層406A，其中第一相連膜層之特徵在於第一導電性。以碳為主之粒子中之各者包含石墨烯片之導電三維(3D)聚集體或黏聚體101B。聚集體可正交熔合在一起以形成開放多孔支架102A來促進沿及跨石墨烯片之接觸點之電傳導。Exemplary methods for producing three-dimensional (3D) carbon-based electrodes, such as the electrodes produced by lithiated carbon support 400A, may include one of the raw materials such as the heat energy transmitted through plasma and/or gaseous supply Or a plurality of plasma-based thermal reactors or torches deposit carbon-based particles 100A or 400A to form a first connected film layer on the substrate, such as the layer 406A shown in FIG. 4A, in which the first connected film The layer is characterized by the first conductivity. Each of the carbon-based particles includes conductive three-dimensional (3D) aggregates or cohesives 101B of graphene sheets. The aggregates can be fused together orthogonally to form an open porous scaffold 102A to promote electrical conduction along and across the contact points of the graphene sheet.

多孔配置形成於開放多孔支架102A中，其中多孔配置有助於接納分散於其中之電解質以用於通過界定擴散路徑109F之互連孔隙，諸如階層式孔隙101A及/或相連微結構107F之Li離子運輸。第一相連膜層之平均厚度不大於約100-200 µm。在一實例中，使黏合劑材料與石墨烯片101B組合以將石墨烯片101B保留在理想位置中來賦予結構以開放多孔支架102A。黏合劑可為或包含熱固性樹脂或可聚合單體，其中在熱、輻射、引發劑、催化劑或其組合輔助之情況下固化樹脂或聚合可聚合單體形成固體樹脂或聚合物。黏合劑可最初為聚合物、煤焦油瀝青、石油瀝青、中相瀝青或有機前驅體材料且稍後熱轉化成碳材料。The porous configuration is formed in the open porous scaffold 102A, where the porous configuration helps to receive the electrolyte dispersed therein for passing through interconnected pores defining the diffusion path 109F, such as the hierarchical pores 101A and/or the Li ions of the connected microstructure 107F transportation. The average thickness of the first connected film layer is not greater than about 100-200 µm. In one example, an adhesive material is combined with the graphene sheet 101B to retain the graphene sheet 101B in a desired position to give the structure to the open porous scaffold 102A. The binder may be or include a thermosetting resin or polymerizable monomer, wherein the resin is cured or polymerized with the aid of heat, radiation, initiator, catalyst, or a combination thereof to form a solid resin or polymer. The binder can be a polymer, coal tar pitch, petroleum pitch, mid-phase pitch, or organic precursor material initially and later thermally converted into a carbon material.

使額外量之以碳為主之粒子100A沈積於第一相連膜層上以於其上形成第二相連膜層，第二相連膜層具有低於第一導電性之第二導電性且更接近電解質414A且遠離可為犧牲基體之集電器定位。Li離子溶液可諸如藉由毛細管灌注作用被浸潤至開放多孔支架102A中以與其表面上之暴露碳反應來促進Li離子解離及電流供應，其中開放多孔支架上之暴露碳可包括大於約100 m² /gm之表面積。An additional amount of carbon-based particles 100A is deposited on the first connected film layer to form a second connected film layer thereon. The second connected film layer has a second conductivity lower than the first conductivity and is closer The electrolyte 414A is located away from the current collector, which can be a sacrificial substrate. The Li ion solution can be infiltrated into the open porous stent 102A, such as by capillary perfusion, to react with the exposed carbon on the surface to promote Li ion dissociation and current supply, wherein the exposed carbon on the open porous stent may include more than about 100 m ² /gm of the surface area.

以碳為主之粒子100A及/或鋰化碳支架400A可在微波反應器中正在運行地合成或在熱反應器內以指代逐層沈積之自下而上方式沈積或生長，且可隨後經由隨後要被乾燥之液體漿料進行澆鑄以形成可適用於實施於或併入Li離子電池內之以碳為主之電極。在一些實例中，此類漿料可包含化學黏合劑及傳導石墨以及電化學活性固有碳。The carbon-based particles 100A and/or lithiated carbon support 400A can be synthesized in operation in a microwave reactor or deposited or grown in a bottom-up manner which refers to layer-by-layer deposition in a thermal reactor, and can be subsequently The liquid slurry to be subsequently dried is cast to form a carbon-based electrode suitable for implementation or incorporation into Li-ion batteries. In some examples, such slurries may include chemical binders and conductive graphite as well as electrochemically active intrinsic carbon.

術語階層式意指其中物品表示為高於彼此位準、低於彼此位準或處於與彼此相同之位準之物品佈置。此處，以碳為主之粒子100A及/或鋰化碳支架400A可藉由以下來生長：在熱反應器中逐層沈積以產生如由傳導性粒子100A、302B及/或402A之膜層406A至412A指示之一或多個級別，該一或多個級別指代藉由整個厚度之鋰化碳支架400A中之電學(指代石墨烯片101B之接觸點)及離子(指代擴散路徑109F)傳導梯度之特定控制產生的級別。各單獨沈積層406A至412A之調諧產生集電器界面處之相對較高導電性及漸進較低自其向外移動之導電性。The term hierarchical refers to the arrangement of items in which items are expressed as being higher than each other, lower than each other, or at the same level as each other. Here, carbon-based particles 100A and/or lithiated carbon scaffold 400A can be grown by depositing layer by layer in a thermal reactor to produce a film such as conductive particles 100A, 302B, and/or 402A 406A to 412A indicate one or more levels, the one or more levels refer to electricity (referring to the contact point of the graphene sheet 101B) and ions (referring to the diffusion path through the entire thickness of the lithiated carbon support 400A 109F) The level produced by the specific control of the conduction gradient. The tuning of each of the individual deposited layers 406A to 412A produces a relatively higher conductivity at the interface of the current collector and a progressively lower conductivity moving outward therefrom.

以碳為主之粒子100A內之石墨烯片101B可藉由傳導電流通過接觸點及/或區域充當電導體且充當用以為諸如372 mAh/g之以其他方式獲自習知石墨陽極之比容量2至3倍之744-1,116 mAh/g之陽極電極比容量提供源的活性Li間夾結構。因此，以碳為主之粒子100A內之石墨烯片之互連3D束102可視為同時致能相對高體積分率之電解活性材料以及有效3D互穿離子及電子路徑之奈米尺度電極。The graphene sheet 101B in the carbon-based particle 100A can act as an electrical conductor by conducting current through the contact points and/or areas and serve as a specific capacity such as 372 mAh/g that is otherwise obtained from conventional graphite anodes 2 Active Li sandwich structure providing source of anode electrode specific capacity up to 3 times 744-1,116 mAh/g. Therefore, the interconnected 3D beam 102 of graphene sheets in the carbon-based particle 100A can be regarded as a nano-scale electrode capable of simultaneously enabling relatively high volume fraction electrolytically active materials and effective 3D interpenetrating ion and electron paths.

此以碳為主之粒子100A之獨特3D結構能夠相對於習知應用而言在其暴露表面處經由電容電荷儲存器儲存電荷以用於所需高功率輸送且亦在其本體內提供法拉第氧化還原離子以用於所需高電能儲存。如一般所理解且如本文中所提及，氧化還原係指還原氧化反應，其中原子氧化態已改變，涉及化學物種之間之電子轉移，其中最常一個物種經歷氧化，而另一物種經歷還原。The unique 3D structure of this carbon-based particle 100A can store charge on its exposed surface via a capacitive charge storage device for high-power delivery and also provide Faraday redox in its body compared to conventional applications. Ions are used for the high electrical energy storage required. As generally understood and as mentioned herein, redox refers to a reductive oxidation reaction, in which the oxidation state of the atom has been changed, and involves the transfer of electrons between chemical species, where most often one species undergoes oxidation and another species undergoes reduction .

如一般所理解且如本文中所提及，法拉第係指發生在製備有及/或以其他方式併有以碳為主之粒子100A之電極表面處之非均相電荷轉移反應。舉例而言，偽電容器法係藉由電極與電解質之間之電子電荷轉移來拉第式儲存電能。此係經由電吸附、氧化還原反應以及間夾方法來實現，稱為偽電容。 用於產生由碳支架產生之電化電池電極之卷軸式處理 As generally understood and as mentioned herein, Faraday refers to a heterogeneous charge transfer reaction that occurs at the surface of an electrode prepared and/or otherwise incorporated with carbon-based particles 100A. For example, the pseudo-capacitor method uses the electric charge transfer between the electrode and the electrolyte to store electric energy in Raday mode. This is achieved through electrosorption, oxidation-reduction reaction, and the intercalation method, which is called pseudo-capacitance. Roll-to-roll processing used to produce electrochemical battery electrodes produced by carbon stents

關於製造(manufacture)，鋰化碳支架400A可經製造以藉由經由卷軸式(R2R)生產方法將一定濃度之以碳為主之粒子100A及/或100E依序、逐層(諸如圖4A中所示之層406A至412A)沈積至諸如集電器之移動基體上來以大規模量製造(fabricate)且/或構建諸如陰極及/或陽極之電化電池電極。藉由類似於離開電漿噴射方法，將3D碳支架結構直接固結在微波反應器外，電極膜可在不需要以其他方式用於漿料澆鑄方法中以用於電池電極之毒性溶劑及黏合劑之情況下連續地產生。因此，可更容易地產生具有受控電學、離子以及化學濃度梯度的採用鋰化碳支架400A之電池電極，該受控電學、離子以及化學濃度梯度係由電漿噴射型方法之逐層依序粒子沈積能力而引起；且諸如摻雜劑之特定元素亦可在不同階段引入電漿沈積過程內。Regarding manufacturing, the lithiated carbon stent 400A can be manufactured to make a certain concentration of carbon-based particles 100A and/or 100E sequentially and layer by layer through a roll-to-roll (R2R) production method (such as in Figure 4A). The illustrated layers 406A to 412A) are deposited on a mobile substrate such as a current collector to fabricate and/or construct electrochemical cell electrodes such as cathodes and/or anodes. By directly consolidating the 3D carbon support structure on the outside of the microwave reactor similar to the off-plasma spraying method, the electrode film can be used for the toxic solvent and bonding of the battery electrode in the slurry casting method without the need for other methods. In the case of the agent, it is produced continuously. Therefore, it is easier to produce battery electrodes using lithiated carbon holder 400A with controlled electrical, ion, and chemical concentration gradients. The controlled electrical, ion, and chemical concentration gradients are sequentially layered by the plasma spray method. It is caused by particle deposition ability; and specific elements such as dopants can also be introduced into the plasma deposition process at different stages.

此外，由於散佈在整個以碳為主之粒子100A中之孔隙105F及/或相連微結構107F，鋰化碳支架400A可以使得其以重力方式(指代用以基於其質量定量測定分析物之分析性化學反應中所使用之方法集合)優於已知裝置之方式製造。亦即，具有界定於整個石墨烯片之3D束102及/或傳導碳粒子104中之孔隙及/或空隙之以碳為主之粒子100A可輕於不具有包括各種孔隙及/或空隙等之中孔結構之相當電池電極。In addition, due to the pores 105F and/or the connected microstructures 107F scattered throughout the carbon-based particles 100A, the lithiated carbon scaffold 400A can make it gravitationally (referring to the analytical ability to quantitatively determine the analyte based on its mass). The set of methods used in chemical reactions) is superior to the known devices. That is, the carbon-based particles 100A having pores and/or voids defined in the 3D beam 102 and/or the conductive carbon particles 104 of the entire graphene sheet can be lighter than those without various pores and/or voids, etc. The mesoporous structure is equivalent to battery electrodes.

以碳為主之粒子100之特點可在於相對於習知技術而言優良之活性材料與非活性材料之比，原因在於相對於非活性及/或結構強化材料而言較大量之活性材料可獲得且經製備以用於通過電傳導。儘管該結構強化材料參與界定以碳為主之粒子100A之一般結構，但可不涉及於或如涉及於石墨烯片之導電互連黏聚體101B中。因此，由於其高活性材料與非活性材料比，以碳為主之粒子100A可展現相對於習知電池而言優良之導電性特性，且在碳可用於置換傳統上使用之較重金屬條件下顯著地輕於該等習知電池。因此，以碳為主之粒子100A可特別充分適合於亦可受益於其相對輕重量之要求高之最終用途應用領域、汽車、輕卡車等。The carbon-based particles 100 can be characterized by an excellent ratio of active materials to inactive materials compared to the prior art, because a larger amount of active materials can be obtained compared to inactive and/or structural strengthening materials. And is prepared for conduction through electricity. Although the structure-strengthening material participates in defining the general structure of the carbon-based particles 100A, it may not be involved or be involved in the conductive interconnection aggregate 101B of the graphene sheet. Therefore, due to its high active material to inactive material ratio, the carbon-based particles 100A can exhibit superior electrical conductivity characteristics compared to conventional batteries, and it is significant under the condition that carbon can be used to replace the heavier metals used traditionally The ground is lighter than those of conventional batteries. Therefore, the carbon-based particles 100A can be particularly well-suited to end-use applications, automobiles, light trucks, etc., which can also benefit from its relatively light weight and high requirements.

以碳為主之粒子100A可經產生以依賴於石墨烯片之導電互連黏聚體101B而獲得滲濾臨限值，該滲濾臨限值係指描述無規系統中之長程連通性形成之滲濾理論中之數學概念。不存在低於臨限值之巨大經連接組件，而存在高於臨限值之約為系統尺寸之巨大組件。因此，石墨烯片之石墨烯導電互連黏聚體之3D束101B可如圖4A中所示自集電器朝向電解質414A傳導電。 卷軸式 (R2R ) 電漿噴射炬沈積系統 The carbon-based particles 100A can be produced to rely on the graphene sheet-based conductive interconnected cohesive 101B to obtain the percolation threshold. The percolation threshold refers to the formation of long-range connectivity in a random system. The mathematical concepts in the infiltration theory. There are no huge connected components below the threshold, but there are huge components about the system size above the threshold. Therefore, the 3D bundle 101B of the graphene conductive interconnection aggregate of the graphene sheet can conduct electricity from the current collector toward the electrolyte 414A as shown in FIG. 4A. Reel type (R2R ) plasma jet torch deposition system

當相對於本發明所揭露之大氣MW電漿反應器之變化用於產生包括整合式相連3D階層式碳支架膜之以粒子為主之輸出物時，噴炬組配可用於產生類似該等以碳為主之結構，諸如由卷軸式(R2R)系統400B顯示之以碳為主之結構。與波導反應器類似，電漿炬准許最初調配材料，隨後加速至可移動或靜止之基體表面上之衝擊區中。R2R方法之各區可提供相異混合相或複合材料合成、調配、固結以及整合(諸如緻密化)之獨特控制。When the change from the atmospheric MW plasma reactor disclosed in the present invention is used to produce a particle-based output including an integrated and connected 3D hierarchical carbon stent film, the torch assembly can be used to produce similar A carbon-based structure, such as the carbon-based structure shown by the reel (R2R) system 400B. Similar to the waveguide reactor, the plasma torch allows the material to be initially blended and then accelerated into the impact zone on the surface of the movable or stationary substrate. Each zone of the R2R method can provide unique control over the synthesis, blending, consolidation, and integration (such as densification) of dissimilar mixed phases or composite materials.

電漿炬可用於在連續移動基體上沈積以碳為主之粒子以在熱電漿噴口位置處致能附加型過程控制，沈積以碳為主之粒子且超出電漿餘輝區到達基體衝擊區。諸如缺陷密度、殘餘應力之各種特性可經由控制膜層之沈積厚度、化學及熱梯度、相變換以及異向性來加以控制。對於電化電池電極製造，大氣MW電漿炬不僅可在不需要諸如NMP之毒性溶劑及/或不使用黏合劑之情況下根據習知漿料澆鑄方法產生經調配且整合之連續3D石墨烯膜，電漿炬亦可用於以經降低成本產生整合式電極/集電器膜結構來獲得經增強效能。The plasma torch can be used to deposit carbon-based particles on a continuously moving substrate to enable additional process control at the position of the thermoplasma nozzle, and deposit carbon-based particles beyond the plasma afterglow zone to reach the substrate impact zone. Various characteristics such as defect density and residual stress can be controlled by controlling the deposition thickness of the film, chemical and thermal gradients, phase transformation and anisotropy. For the production of electrochemical battery electrodes, the atmospheric MW plasma torch can not only produce a formulated and integrated continuous 3D graphene film according to the conventional slurry casting method without the need for toxic solvents such as NMP and/or without the use of adhesives. The plasma torch can also be used to generate an integrated electrode/collector membrane structure with reduced cost to obtain enhanced performance.

圖4B顯示採用諸如422B、424B、426B及/或428B之電漿噴射炬422B至428B之群組444B之例示性佈置之卷軸式(R2R)系統400b，以上所有者均經組配以執行逐層沈積來逐漸地製造(在其他方面稱為生長)圖3B中所示之以碳為主之支架300B及/或其變異形式。電漿噴射炬414B至420B之群組444B被以連續順序定向於R2R處理設備440B上方，該R2R處理設備440B可包括經組配以分別在相同方向430B及432B旋轉之輪及/或卷軸434B及439B，以引起犧牲層402B之轉變向前運動436B，在該犧牲層402B上碳支架436B之層442B可以逐層方式沈積以達成與每單位體積之各漸進性沈積層(諸如膜層406A-412A)中之區域所含有之以碳為主之粒子100A之濃度位準成比例的分級電學傳導梯度。Fig. 4B shows an exemplary arrangement of the reel-to-reel (R2R) system 400b of the group 444B of plasma jet torches 422B to 428B such as 422B, 424B, 426B, and/or 428B. The above owners are all configured to perform layer by layer Deposited to gradually manufacture (in other respects referred to as growth) the carbon-based scaffold 300B shown in FIG. 3B and/or its variant form. The group 444B of plasma jet torches 414B to 420B is oriented in a continuous sequence above the R2R processing device 440B. The R2R processing device 440B may include wheels and/or reels 434B and 439B, to cause the transformation of the sacrificial layer 402B to move forward 436B. On the sacrificial layer 402B, the layer 442B of the carbon support 436B can be deposited layer by layer to achieve a progressive deposition layer per unit volume (such as film layers 406A-412A). A graded electrical conduction gradient proportional to the concentration level of the carbon-based particles 100A contained in the area in ).

該沈積可涉及在犧牲層402B上安置碳支架300B之如圖4B中所示之電漿噴射炬414B至420B之群組444B，最初在向前運動436B之方向，噴炬414B在向下方向，自原料供應管線412B開始朝向犧牲層404B延伸最遠，該噴炬414B經定位以噴射422B以碳為主之材料來沈積最初層404B，該最初層404B亦可在圖4A中顯示為中間層406A，諸如此類。最初層404B可經沈積以達成最高傳導性值，其中後續層406B至410B中之各者之特點在於用以達成用於層442B之分級電梯度之構成以碳為主之支架300B之以碳為主之粒子100A的成比例地不太緻密之分散。The deposition may involve placing a carbon support 300B on the sacrificial layer 402B of the plasma spray torch 414B to 420B group 444B as shown in FIG. 4B, initially in the direction of forward movement 436B, and torch 414B in the downward direction, The torch 414B is positioned to spray 422B with a carbon-based material to deposit the initial layer 404B. The initial layer 404B can also be shown as an intermediate layer 406A in FIG. 4A. , And so on. The initial layer 404B can be deposited to achieve the highest conductivity value, and each of the subsequent layers 406B to 410B is characterized in that it is used to achieve the grading elevation structure for the layer 442B. The carbon-based bracket 300B uses carbon as the The main particles 100A are proportionally less densely dispersed.

亦即，如圖4B中所示，電漿噴射炬414B至420B可經定向以具有逐漸地降低或以其他方式變化之高度，以使得來自群組444B之各噴炬可經調諧以噴射(分別為噴射422B至428B)由原料供應管線412B供應之以碳為主之原料材料噴射物。因此，可更容易地產生具有受控電學、離子以及化學濃度梯度之電池電極，該受控電學、離子以及化學濃度梯度係由關於電漿噴射炬系統400B的本文所描述之逐層依序沈積而引起，該電漿噴射炬系統400B呈現電漿噴射型方法之所需特點；且特定元素或額外成分亦可在不同階段在由電漿噴射炬系統400B描述之以電漿為主之噴射沈積過程內引入。該控制可延伸至電漿噴射炬系統400B之可調諧性以達成層442B中之任一個或多個之目標電場及/或電磁場特性。That is, as shown in FIG. 4B, the plasma jet torches 414B to 420B can be oriented to have a height that gradually decreases or otherwise changes, so that each torch from the group 444B can be tuned to jet (respectively To spray 422B to 428B) the carbon-based raw material spray supplied from the raw material supply line 412B. Therefore, it is easier to produce battery electrodes with controlled electrical, ion, and chemical concentration gradients that are sequentially deposited layer by layer as described herein with respect to the plasma jet torch system 400B As a result, the plasma jet torch system 400B exhibits the required characteristics of the plasma jet type method; and specific elements or additional components can also be deposited at different stages in the plasma-based jet deposition described by the plasma jet torch system 400B Introduced in the process. This control can be extended to the tunability of the plasma jet torch system 400B to achieve the target electric field and/or electromagnetic field characteristics of any one or more of the layers 442B.

電漿噴射炬414B至420B之群組444B可採用以電漿為主之熱增強碳噴射技術以提供其中經熔融或加熱材料被噴射至表面上之碳塗佈過程。為塗料前驅體之原料係藉由電學、電漿或電弧或化學手段(諸如燃燒及/或火燒)來加熱。The group 444B of the plasma jet torches 414B to 420B can adopt a plasma-based heat-enhanced carbon jet technology to provide a carbon coating process in which molten or heated materials are jetted onto the surface. The raw material, which is the coating precursor, is heated by electricity, plasma, electric arc, or chemical means (such as combustion and/or fire).

如與諸如電鍍、物理及化學氣相沈積之其他塗佈方法相比，藉由電漿噴射炬414B至420B進行之熱噴射可視方法及原料而在大區域上以高沈積速率提供厚度大致介於20 µm或更大至若干mm範圍內之厚塗層。可供用於熱噴射之塗佈材料包括金屬、合金、陶瓷、塑膠以及複合材料。其被以粉末或金屬絲形式進料，加熱至熔融或半熔融狀態，且以微米尺寸粒子之形式加速朝向基體。燃燒或電弧放電通常用作熱噴射之能量源。所得塗料係藉由積聚許多所噴射粒子來製造。表面可不顯著地變熱，允許塗佈可燃物質。As compared with other coating methods such as electroplating, physical and chemical vapor deposition, thermal spraying by plasma spray torches 414B to 420B can provide a thickness of approximately between Thick coating in the range of 20 µm or more to several mm. Coating materials available for thermal spraying include metals, alloys, ceramics, plastics and composite materials. It is fed in the form of powder or wire, heated to a molten or semi-molten state, and accelerated toward the substrate in the form of micron-sized particles. Combustion or arc discharge is commonly used as an energy source for thermal injection. The resulting paint is produced by accumulating many sprayed particles. The surface can heat up insignificantly, allowing the coating of combustible substances.

塗層品質通常藉由量測其孔隙度、氧化物含量、大硬度及微硬度、黏合強度及表面粗糙度來評估。一般而言，塗層品質隨粒子速度增大而提高。 實施於 Li S 二次電池中之碳支架 Coating quality is usually evaluated by measuring its porosity, oxide content, large and micro hardness, bonding strength and surface roughness. Generally speaking, the quality of the coating increases as the particle velocity increases. Carbon stent implemented in Li S secondary battery

電漿噴射炬414B至420B之群組444B可經組配或調諧來以受控方式噴射以碳為主之材料以達成特定所需階層式且經組織結構，諸如適用於視以碳為主之粒子100A及/或100E之孔隙度百分比而定經由毛細管作用進行之於其中之Li離子浸潤的以碳為主之粒子100A及/或100E之開放多孔支架102A及相連微結構107F。能夠被灌注至相連微結構107F中且/或沈積於以碳為主之粒子100A及/或100E之暴露表面區域及其他該等類似結構上之S之總量可亦視其孔隙度百分比而定，其中3D碎片形結構提供諸如孔隙105F之較大孔隙，各孔隙具有可在電化電池操作期間有效地收納且微米限制S達所需時段之尺寸103F。存在准許在限制S以諸如0-5%、0-10%、0-30%、0-40%、0-50%、0-60%、0-70%、0-80%、0-90%及/或0-100%之經界定百分比為目標之情況下純藉由設計且生長結構S來組合S以防止任何所得聚硫化物(PS)遷移至孔隙105F之外的實例，該等百分比範圍中之任一者或多者成功地顯示聚硫化物遷移至電極結構之外之延緩。 實施於 Li 空氣二次電池中之碳支架 The group 444B of plasma jet torches 414B to 420B can be configured or tuned to inject carbon-based materials in a controlled manner to achieve a specific desired hierarchical and organized structure, such as suitable for carbon-based materials The porosity percentage of the particles 100A and/or 100E depends on the open porous scaffold 102A and the connected microstructure 107F of the carbon-based particles 100A and/or 100E in which Li ions are infiltrated by capillary action. The total amount of S that can be impregnated into the connected microstructure 107F and/or deposited on the exposed surface area of the carbon-based particles 100A and/or 100E and other similar structures can also depend on its porosity percentage , Where the 3D fragmented structure provides larger pores such as pores 105F, each pore having a size 103F that can be effectively received during the operation of the electrochemical cell and the micrometer limits S for a desired period of time. There is permission to limit S such as 0-5%, 0-10%, 0-30%, 0-40%, 0-50%, 0-60%, 0-70%, 0-80%, 0-90 % And/or a defined percentage of 0-100% is an example of purely combining S by designing and growing the structure S to prevent any resulting polysulfide (PS) from migrating outside of the pore 105F. These percentages Any one or more of the ranges successfully demonstrated the delay of the migration of the polysulfide to the outside of the electrode structure. Carbon stent implemented in Li- air secondary battery

實存Li空氣陰極可持續僅3-10個循環，且因此尚未被普遍地理解提供極有前景或可靠之技術。在該等陰極中，空氣自身充當陰極，因此流過陰極，諸如流過孔隙、流孔或其他開口之空氣之可靠且穩健供應當前有效地排除諸如智慧型手機之消費者級可攜電子裝置中之現實應用。Existing Li air cathodes can last only 3-10 cycles, and therefore have not been universally understood to provide extremely promising or reliable technology. In these cathodes, the air itself acts as the cathode, so the reliable and stable supply of air flowing through the cathode, such as through pores, orifices or other openings, is currently effectively excluded from consumer-grade portable electronic devices such as smartphones The real application.

裝置可用某種空氣泵送機制來製造，但鑒於盛行於空氣中之任何量之雜質可且將與可獲得Li在寄生副反應中反應，最終減小總體電化電池之比容量，空氣純化仍為問題。此外，空氣僅提供僅約20.9% O₂ ，且因此不與其他替代性當前高級電池技術一樣有效。The device can be manufactured by some kind of air pumping mechanism, but in view of the fact that any amount of impurities prevailing in the air can and will react with the available Li in a parasitic side reaction, and ultimately reduce the specific capacity of the overall electrochemical battery, air purification is still problem. In addition, air only provides only about 20.9% O ₂ and therefore is not as effective as other alternative current advanced battery technologies.

儘管如此，甚至鑒於上文所提及之挑戰，上文所提供之關於實施於碳支架300B及/或鋰化碳支架400A中之以碳為主之粒子100A、100E及/或其任何變異形式之實例可經組配以在3D印刷電池中運作。值得注意地，可採取措施以防護，諸如藉由調諧以在開放多孔支架102A之特定靶向區域中達成所需結構強化，以防止不合需要且/或突發之多孔結構塌陷，以便避免產生界定於其中之通路阻塞。在實例中，碳支架300B可經無數金屬氧化物裝飾以達成該強化，一旦鋰與空氣反應以自發地自彼狀態形成固體，則此舉亦可控制或以其他方式積極貢獻於結構自身之機械穿隧等。諸如不進行關於所揭露之以碳為主之粒子100A及/或其類似物以及Li空氣陰極之實施之特殊製備之傳統情形可以其他方式涉及Li離子與以氣態形式提供之碳反應以使得Li離子及含碳氣體反應以形成膨脹固體。且視此擴增發生位置而定，可機械地降解諸如碳支架300B之總體以碳為主之中孔支架結構。 製備以碳為主之粒子以進行鋰化 Nevertheless, even in view of the challenges mentioned above, the above provides about the carbon-based particles 100A, 100E and/or any variants thereof implemented in the carbon scaffold 300B and/or lithiated carbon scaffold 400A The example can be configured to operate in a 3D printed battery. It is worth noting that measures can be taken to protect, such as by tuning to achieve the desired structural reinforcement in the specific target area of the open porous scaffold 102A, to prevent undesirable and/or sudden collapse of the porous structure, so as to avoid delimitation The passage in it is blocked. In an example, the carbon stent 300B can be decorated with numerous metal oxides to achieve this strengthening. Once lithium reacts with air to spontaneously form a solid from the other state, this action can also be controlled or otherwise actively contributes to the mechanism of the structure itself. Tunneling and so on. For example, the traditional case of not performing special preparations regarding the implementation of the disclosed carbon-based particles 100A and/or its analogues and Li air cathodes may involve the reaction of Li ions with carbon provided in gaseous form in other ways to make Li ions And the carbon-containing gas react to form an expanded solid. And depending on the location where the amplification occurs, the overall carbon-based mesoporous scaffold structure such as the carbon scaffold 300B can be mechanically degraded. Preparation of carbon-based particles for lithiation

為在當前氧化鋰化合物陰極上致能替代性非Li或鋰化以碳為主之支架型陰極，諸如限制硫、氧及氧化釩之替代性非Li或鋰化以碳為主之支架型陰極，以及為適應當前Li離子電池中之第一電荷鋰損失、所得經降低庫倫效率，可需要用於意欲實施於電化電池電極中之以碳為主之結構化之可升級預鋰化方法。因此，已對以碳為主之粒子100A、100E及/或包括碳支架300B之基於其之任何衍生結構進行各種實驗嘗試，諸如球磨碾磨、後熱退火以及自額外電極開始之電化還原。該等成果已用於預鋰化，諸如以化學方式製備以碳為主之結構以與鋰進行物理及/或化學反應且/或物理上及/或化學上限制鋰，但已滿足均一性、鋰反應性、成本以及可升級性挑戰。To enable alternative non-Li or lithiated carbon-based scaffold cathodes on current lithium oxide compound cathodes, such as alternative non-Li or lithiated carbon-based scaffold cathodes that restrict sulfur, oxygen and vanadium oxide , And in order to adapt to the loss of first charge lithium in current Li-ion batteries and the resulting reduced Coulombic efficiency, a scalable pre-lithiation method for carbon-based structuring intended to be implemented in electrochemical battery electrodes may be required. Therefore, various experimental attempts have been made on the carbon-based particles 100A, 100E and/or any derivative structure based on the carbon scaffold 300B, such as ball milling, post thermal annealing, and electrochemical reduction starting from additional electrodes. These results have been used for pre-lithiation, such as chemically preparing carbon-based structures to physically and/or chemically react with lithium and/or physically and/or chemically restricting lithium, but the uniformity, Lithium reactivity, cost, and scalability challenges.

儘管如此，如先前實質上所論述，藉由微調反應器過程參數，以碳為主之粒子100A、100E及/或碳支架300B可藉由逐層沈積方法來合成及/或製造以充當具有經工程改造之表面化學反應，諸如包括氮及氧摻雜來促進涉及歧化之氧化物快速分解的以碳為主之主體結構。Nevertheless, as previously discussed substantially, by fine-tuning the reactor process parameters, the carbon-based particles 100A, 100E and/or the carbon scaffold 300B can be synthesized and/or manufactured by a layer-by-layer deposition method to serve as Engineered surface chemical reactions, such as carbon-based host structures that include nitrogen and oxygen doping to promote the rapid decomposition of oxides involved in disproportionation.

在可包括一或多個火花形成之熱活化時，Li金屬可自發地，諸如無壓力梯度且非被動地由毛細管力驅動進行浸潤以產生受控預鋰化碳結構或粒子構建區塊。隨後，該等預鋰化粒子構建區塊可合成為具有分級導電性之整合式複合膜，該分級導電性係自： ●            在諸如由中間層406A顯示之與集電器接觸之後平面處之高傳導性，至 ●            在電解質/電極平面處之絕緣離子傳導層。 如可與Li金屬之非反應性浸潤相關之表面化學性質可藉由經由使用熱重分析(TGA)或差示掃描量熱法DSC分析性技術來最佳化氧化物熱還原度(諸如放熱)而得到調諧。During thermal activation, which may include one or more spark formation, Li metal can spontaneously, such as without pressure gradient and passively driven by capillary force, infiltrate to produce controlled prelithiated carbon structures or particle building blocks. Subsequently, the pre-lithiated particle building blocks can be synthesized into an integrated composite film with hierarchical conductivity, which is derived from: ● The high conductivity of the plane after contact with the current collector, such as shown by the middle layer 406A, to ● Insulating ion conductive layer at the electrolyte/electrode plane. For example, the surface chemical properties related to the non-reactive infiltration of Li metal can be optimized by using thermogravimetric analysis (TGA) or differential scanning calorimetry DSC analytical techniques to optimize the degree of thermal reduction of oxides (such as exotherm) And get tuned.

為解決如可與自低體積實驗室測試及樣品產生環境過渡至能夠同時滿足多個客戶訂單之大體積大規模工廠相關之可擴展性問題，上文所描述之預鋰化方法可與諸如硬焊之其他液體熔融潤濕方法類似易於適應於連續卷軸式(R2R)格式。In order to solve the scalability problems associated with the transition from low-volume laboratory testing and sample production environments to large-volume large-scale factories that can meet multiple customer orders at the same time, the pre-lithiation method described above can be combined with hardware Other liquid melting and wetting methods for welding are similar and easy to adapt to continuous roll-to-roll (R2R) format.

在噴炬方法之情況下在受控熱乾環境中，可在一些組配中包括鉭(Ta)或銅(Cu)之薄膜Li包覆箔可被負載至加熱砑光卷軸上，以接觸以碳為主之粒子100A或碳膜。諸如浸泡之熱滯留、時間、梯度以及所施加壓力可經調節及控制以促進以下二者：(1)活化；以及(2)浸潤處理步驟。 引發碳支架鋰化 In the case of the torch method in a controlled heat and dry environment, a thin-film Li-coated foil that can include tantalum (Ta) or copper (Cu) in some combinations can be loaded on a heating calender reel to contact with Carbon-based particles 100A or carbon film. Heat retention, time, gradient, and applied pressure such as soaking can be adjusted and controlled to promote both: (1) activation; and (2) soaking treatment steps. Initiate lithiation of carbon stents

在將Li金屬灌注方法發展至以碳為主之結構及/或聚結粒子中之前，已努力評估以下二個情境： ●            生長具有經延伸D-間距之微波石墨烯片，該經延伸D-間距允許以比發生在典型市售石墨烯片中之Li間夾高得多之效率或更快之速率使Li間夾發生在個別石墨烯片之間；且以成功地且可重複地達成該較高de-間距之方式生長FLG；以及 ●            使用傳送至由以碳為主之粒子100A及/或100E之開放多孔支架102A界定之階層式孔隙101A及/或相連微結構107F中之濕液體Li金屬正面，其中相對於以其他方式官能化暴露以碳為主之表面而言Li金屬至暴露以碳為主之表面至濕之吸引力相同。 本發明所揭露之熱反應器可執行後處理以產生高度經組織且結構化碳，該等高度經組織且結構化碳運作與熔融Li金屬及/或其他物種浸潤，諸如鋁向碳化矽燒結材料中之浸潤相關且在無來自外部源之額外壓力之情況下錘擊粒子表面以促進熔融(Li)金屬正面浸潤。該等努力准許連續潤濕代替使用毛細管壓力以將金屬推送至以碳為主之粒子100A及/或100E之開放多孔支架102A中。Before the development of Li metal infusion methods into carbon-based structures and/or coalesced particles, efforts have been made to evaluate the following two scenarios: ● Growing microwave graphene sheets with extended D-spacing that allows Li intercalation at a much higher efficiency or faster rate than Li intercalation that occurs in typical commercially available graphene sheets Occurs between individual graphene sheets; and grows FLGs in a way that successfully and reproducibly achieves the higher de-spacing; and ● Use the wet liquid Li metal front surface of the layered pore 101A defined by the open porous scaffold 102A defined by the carbon-based particles 100A and/or 100E and/or the connected microstructure 107F, which is compared with other methods of functionalization The attraction of Li metal to the exposed carbon-based surface to wet is the same. The thermal reactor disclosed in the present invention can perform post-processing to produce highly organized and structured carbon, which operates with molten Li metal and/or other species infiltration, such as aluminum to silicon carbide sintered material Infiltration is related and hammers the particle surface without additional pressure from an external source to promote the front-side infiltration of molten (Li) metal. These efforts permit continuous wetting instead of using capillary pressure to push metal into the open porous scaffold 102A of carbon-based particles 100A and/or 100E.

圖4A顯示由與以碳為主之粒子100A及/或100E形式及功能類似之若干互連以碳為主之粒子402A形成、在膜層406A至412A中以變化濃度位準自最高濃縮至最低濃縮合成且沈積的鋰化碳支架。膜層406A至412A全部均經組配以經由非反應性毛細管灌注方法浸潤有呈液態或於液相中之熔融Li金屬及/或Li離子溶液以在石墨烯片101B之石墨烯片對之間間夾Li離子。大致1 Å至3 Å之例示性D-間距可在石墨烯片101B合成期間為目標以將比習知石墨烯片堆疊更多之Li離子保留在交替石墨烯片之間。Figure 4A shows the formation of a number of interconnected carbon-based particles 402A similar in form and function to the carbon-based particles 100A and/or 100E. The film layers 406A to 412A are concentrated from the highest to the lowest with varying concentration levels. Concentrate the synthesized and deposited lithiated carbon scaffold. The membrane layers 406A to 412A are all assembled to be infiltrated with molten Li metal and/or Li ion solution in a liquid or in a liquid phase by a non-reactive capillary infusion method to be between the graphene sheet pairs of the graphene sheet 101B Li ions are sandwiched in between. An exemplary D-spacing of approximately 1 Å to 3 Å can be targeted during graphene sheet 101B synthesis to retain more Li ions between alternating graphene sheets than conventional graphene sheet stacks.

鄰接及/或接觸以碳為主之粒子402A之間指代空區域或空間之空隙416A可由遠離集電器420A且面向液相電解質層、鈍化層418A定位之鋰化碳支架400A之部分界定。鈍化意指材料變得被動，亦即，不太受未來使用環境影響或腐蝕。另外或可替代地，Li離子傳導絕緣或分級中間相層可諸如在鈍化層418A之同一位置處，面向電解質414A沈積於層412A上以使與自由及/或物理上及/或化學上未連接之呈離子形式之Li之副反應減至最少。The void 416A referring to the empty region or space between adjacent and/or contacting the carbon-based particles 402A can be defined by the portion of the lithiated carbon support 400A positioned away from the current collector 420A and facing the liquid electrolyte layer and the passivation layer 418A. Passivation means that the material becomes passive, that is, less affected or corroded by the future use environment. Additionally or alternatively, a Li ion conductive insulating or graded intermediate phase layer may be deposited on layer 412A, such as at the same location as passivation layer 418A, facing electrolyte 414A so as to be freely and/or physically and/or chemically unconnected. The side reaction of Li in the form of ions is minimized.

如由熔融Li金屬所提供之任何該被蓋層Li在沈積或置放之前可以液態形式流動至由以碳為主之粒子402A界定之空隙416A中以輔助形成與膜層406A-412A各層中之以碳為主之粒子402A之濃度位準成比例的電化梯度。As provided by molten Li metal, any of the capping layer Li can flow in liquid form into the void 416A defined by the carbon-based particles 402A before deposition or placement to assist in the formation of the film layers 406A-412A. An electrochemical gradient proportional to the concentration level of the carbon-based particles 402A.

二次電池中之重複或循環Li離子電極(諸如陽極或陰極)使用可能會導致由熔融Li金屬使用所致之問題，諸如在電鍍操作中再沈積期間之體積擴增，該等電鍍操作意指使用電流以減少經溶解金屬陽離子以使得其在電極上形成薄相干金屬塗層的過程。該術語亦可用於陰離子至固體基體上之電學氧化，如同用於製造銀/氯化銀電極之銀金屬絲上之氯化銀形成一樣。Repeated or cyclic use of Li ion electrodes (such as anodes or cathodes) in secondary batteries may cause problems caused by the use of molten Li metal, such as volume increase during re-deposition in electroplating operations, which means Electric current is used to reduce the process of dissolving metal cations so that they form a thin coherent metal coating on the electrode. The term can also be used for the electrical oxidation of anions onto a solid substrate, as is the formation of silver chloride on silver wires used to make silver/silver chloride electrodes.

與Li離子溶液浸潤至鋰化碳支架400A中相關之電鍍中所使用之方法可稱為電沈積，亦稱為電泳沈積(EPD)，且與逆向作用之濃差電池類似。如上文所描述之Li離子電鍍可能會導致約為鋰化碳支架400A之400%或更大之體積擴增。自穩定性觀點來看，此類擴增為非微機械地所需的且造成許多無效區衰退，該等無效區係指非活性區域或非化學上及/或電學上活化區域，因此最終防止如此裝備之Li離子電池之外之較長壽命衍生。一般而言，需要具有大量Li離子材料板，此意謂還原至平滑且均一表面上以因此促進Li離子之均一沈積。在平滑平坦界面中移除亦為平滑的。The method used in electroplating related to the infiltration of Li ion solution into the lithiated carbon support 400A can be called electrodeposition, also called electrophoretic deposition (EPD), and is similar to a reverse-acting concentration cell. The Li ion plating as described above may result in a volume increase of about 400% or more of the lithiated carbon stent 400A. From the standpoint of stability, such amplification is not required for micromechanically and causes many ineffective regions to degenerate. These ineffective regions refer to inactive regions or non-chemically and/or electrically activated regions, thus ultimately preventing The longer life span is derived from the Li-ion battery equipped in this way. Generally speaking, it is necessary to have a large number of Li ion material plates, which means reduction to a smooth and uniform surface to thereby promote uniform deposition of Li ions. The removal is also smooth in a smooth flat interface.

在實踐中，Li在被浸潤至碳支架400A中時可傾向於形成不合需要之樹枝狀結晶，該等樹枝狀結晶定義為以典型多分支樹狀形式發展之晶體。亦呈針狀Li離子樹枝狀結晶(針狀係描述由細長針狀晶體沈積物構成之晶體慣態)之形式之該等Li離子樹枝狀結晶遠離表面生長，在該等表面上，諸如在個別石墨烯片101B上及/或在其之間浸潤Li離子。在一些情況下，在足夠電池充電-放電循環之情況下，樹枝狀突起或隆凸可自電化電池內併有鋰化以碳為主之支架400A之陽極至與以碳為主之支架相對定位之陰極一路生長以造成短路線或短路，描述此時向電路供應電力之二個導體之間存在低阻力連接。此舉可在電力源中生成過量電壓串流且造成過量電流流動。電流過短路線且造成短路。In practice, Li may tend to form undesirable dendrites when being infiltrated into the carbon scaffold 400A, and these dendrites are defined as crystals that develop in a typical multi-branched dendritic form. These Li ion dendrites, also in the form of needle-like Li ion dendrites (needles describe the habit of crystals composed of slender needle-like crystal deposits) grow away from the surface, on these surfaces, such as in individual The graphene sheet 101B is infiltrated with Li ions and/or between them. In some cases, with sufficient battery charge-discharge cycles, the dendrites or bulges can self-electrify the battery and have the anode of the lithium-based carbon-based stent 400A to be positioned relative to the carbon-based stent The cathode grows all the way to cause a short circuit or short circuit, which describes the low resistance connection between the two conductors that supply power to the circuit at this time. This can generate excessive voltage strings in the power source and cause excessive current to flow. Current flows through the short-circuit wire and causes a short circuit.

毛細管Li離子灌注至鋰化碳支架400A技術可解決許多所描述問題。然而，Li離子電池中遇到的持續問題包含習知陰極僅提供有限數量的比容量或比能能力。同樣，在陽極側上，亦已觀測到比容量及比能密度降低。因此，即使考慮到相對合乎需要之程度，就電能儲存容量及電流輸送而言，Li離子電池亦可與Li金屬氫化物或鉛酸或Ni Cad電池比較，當併入本發明所揭露之以碳為主之材料中的任一者或多者(諸如鋰化以碳為主之支架400A)之後，就對抗或防止不合需要之以鋰為主之樹枝狀結晶形成的保護，甚至電力儲存及輸送方面具有更大進步，以接近具有約3,800 mAh/g之比容量的純Li金屬之理論容量。Capillary Li ion infusion into the lithiated carbon stent 400A technology can solve many of the described problems. However, persistent problems encountered in Li-ion batteries include that conventional cathodes only provide a limited amount of specific capacity or specific energy capacity. Similarly, on the anode side, a decrease in specific capacity and specific energy density has also been observed. Therefore, even considering the relatively desirable degree, in terms of electric energy storage capacity and current transmission, Li ion batteries can be compared with Li metal hydride or lead acid or Ni Cad batteries. After any one or more of the main materials (such as lithiated carbon-based stent 400A), it can resist or prevent undesirable protection from the formation of lithium-based dendrites, and even power storage and transmission It has made greater progress in order to approach the theoretical capacity of pure Li metal with a specific capacity of about 3,800 mAh/g.

已進行其他方法，包括研發固態電池，完全未涉及液相。然而，由於使用氧化電解質來達成且穩定與鋰接觸，因此注意力回至Li金屬。且亦探索包括Si、Sn及各種其他合金之Li金屬的替代物。然而，即使在消除Li金屬後，仍可需要Li離子源。Other methods have been carried out, including the development of solid-state batteries, which do not involve liquid phase at all. However, due to the use of an oxidizing electrolyte to achieve and stabilize contact with lithium, attention has been returned to Li metal. And also explored alternatives to Li metals including Si, Sn and various other alloys. However, even after eliminating Li metal, a Li ion source may still be required.

Li離子電池電極結構中之鋰材料的替代材料可產生以下能量密度值：氧化物提供260 mAh/g；且硫(S)提供650 mAh/g。由於其相對較高的能量密度能力，因此電池電極應用中需要限制硫(S)，因此其不被溶解(solubilize/dissolve)於周圍電解質中。為達此效果，需要對硫微米限制，如先前關於開放多孔支架102A之相連微結構107F (如圖1F中所示)之孔隙105F所描述。限制(或微米限制)液體意指在奈米尺度下受到幾何限制之液體，使得大部分分子足夠接近界面以感測與標準體條件之某一差異。典型實例為在多孔介質中之液體或在溶合殼中之液體。Alternative materials for lithium materials in the electrode structure of Li-ion batteries can produce the following energy density values: oxide provides 260 mAh/g; and sulfur (S) provides 650 mAh/g. Due to its relatively high energy density capability, it is necessary to limit sulfur (S) in battery electrode applications, so it is not solubilized/dissolved in the surrounding electrolyte. In order to achieve this effect, the sulfur micron restriction is required, as previously described with respect to the pore 105F of the connected microstructure 107F (as shown in FIG. 1F) of the open porous scaffold 102A. Confinement (or micron confinement) liquid refers to a liquid that is geometrically constrained at the nanometer scale, so that most of the molecules are close enough to the interface to sense a certain difference from the standard body condition. Typical examples are liquids in porous media or liquids in fusion shells.

限制及/或微米限制指代在微觀尺寸區域內的限制有規律地防止結晶，其使得液體能夠在其均相成核溫度以下進行過冷，即使此在散裝狀態下為不可能的。因此，鑒於上文呈現之各種挑戰及此處未論述之其他挑戰，可藉由替代地利用少層石墨烯(FLG)材料及/或結構(定義為具有低於15層之石墨烯生長、沈積或以其他方式組織於堆疊架構中，其中Li離子以經界定間隔及/或濃度位準間夾於堆疊支架之間)來達成以傳統石墨烯為主之陽極的各種改進。可如此製備以碳為主之粒子100A、100E及/或其類似者中之任一者或多者。Confinement and/or micron confinement refers to confinement within the microscopic size region that regularly prevents crystallization, which enables the liquid to be supercooled below its homogeneous nucleation temperature, even if this is not possible in the bulk state. Therefore, in view of the various challenges presented above and other challenges not discussed here, it is possible to alternatively use few-layer graphene (FLG) materials and/or structures (defined as graphene growth and deposition with less than 15 layers). Or organized in a stacked structure in other ways, in which Li ions are sandwiched between stacked supports at defined intervals and/or concentration levels) to achieve various improvements to traditional graphene-based anodes. Any one or more of carbon-based particles 100A, 100E, and/or the like can be prepared in this way.

如此，自石墨至FLG，可使間夾有Li之以碳為主之結構之比容量自約380增至超過1,000 mAh/g。所揭露材料可用FLG置換石墨，以准許更高的活性表面積且可增大個別石墨烯層之間的間距，以浸潤至多2至3個Li離子，而其他地方通常可見僅1個Li離子，如藉由圖1I所示，表示可根據間距來控制各種石墨或石墨烯層平面，以達成在鄰近石墨或石墨烯層平面之間的Li離子之各種擬合。In this way, from graphite to FLG, the specific capacity of the carbon-based structure with Li interposed can be increased from about 380 to more than 1,000 mAh/g. The disclosed material can replace graphite with FLG to allow a higher active surface area and increase the spacing between individual graphene layers to infiltrate up to 2 to 3 Li ions, while only 1 Li ion is usually seen elsewhere, such as As shown in FIG. 1I, it is shown that various graphite or graphene layer planes can be controlled according to the pitch to achieve various fittings of Li ions between adjacent graphite or graphene layer planes.

在石墨烯中，每個石墨烯片中之六邊形碳結構可保持定位於彼此之頂部上，此被稱作A-A封裝順序而非A-B封裝順序。例示性碳封裝順序顯示於圖1H中所示之化學結構圖中，其中Li離子可擬合於由以六角晶格結構佈置及結合之碳原子界定的空隙中。特定而言，設想石墨烯片及/或少層石墨烯(FLG)之組配，其中石墨烯之個別層可直接堆疊於彼此之頂部，以得到彼此不相稱、不對稱及/或以其他方式不規則的堆疊，如圖1I中之階段3所示，其又准許在FLG結構之每個石墨烯層之間添加間夾的Li離子。In graphene, the hexagonal carbon structures in each graphene sheet can remain positioned on top of each other, which is called the A-A packaging sequence instead of the A-B packaging sequence. An exemplary carbon encapsulation sequence is shown in the chemical structure diagram shown in FIG. 1H, in which Li ions can be fitted in voids defined by carbon atoms arranged and bonded in a hexagonal lattice structure. Specifically, imagine a combination of graphene sheets and/or few-layer graphene (FLG), in which individual layers of graphene can be directly stacked on top of each other to obtain disproportionate, asymmetrical, and/or other ways Irregular stacking, as shown in stage 3 in Figure 1I, in turn permits the addition of intercalated Li ions between each graphene layer of the FLG structure.

在傳統條件及情況下，在分層石墨烯結構中自上至下或由下而上***Li離子在實務上可能極其困難。相當地，Li離子更易於***於由可界定距離分隔之個別石墨烯層之間。因此，關鍵在於管理且調諧多少可用的邊緣區域。在彼方面，本文所揭露之以碳為主之結構中之任一者可如此調諧。且石墨烯中之碳亦具有傳導性，因此此特徵藉由以下方式提供雙重作用：(1)為FLG支架電極結構，諸如碳支架300B及/或鋰化碳支架400A提供結構界定；及(2)於其中之傳導路徑。Under traditional conditions and circumstances, it may be extremely difficult to insert Li ions from top to bottom or bottom to top in the layered graphene structure. Correspondingly, Li ions are more easily inserted between individual graphene layers separated by a definable distance. Therefore, the key is to manage and tune how much of the available edge area. In that respect, any of the carbon-based structures disclosed in this article can be so tuned. And the carbon in graphene is also conductive, so this feature provides a dual role by: (1) providing structure definition for FLG stent electrode structures, such as carbon stent 300B and/or lithiated carbon stent 400A; and (2) ) The conduction path in it.

用於製造本文所揭露之以碳為主之結構中之任一者或多者的製造技術可表明，需要相對於其平坦表面調節個別石墨烯層邊緣長度；此外，調節個別石墨烯堆疊之間的間距可為可能的。石墨烯(以其二維結構)必需提供顯著更多的表面積，其中可***Li離子。因此，根據本文中所揭露之主題的各種態樣應用石墨烯片可在增強的能量儲存密度之方向上提供自然演變。The manufacturing technology used to manufacture any one or more of the carbon-based structures disclosed herein may indicate that the edge length of the individual graphene layers needs to be adjusted relative to its flat surface; in addition, the adjustment between the individual graphene stacks The spacing may be possible. Graphene (with its two-dimensional structure) must provide significantly more surface area into which Li ions can be inserted. Therefore, the application of graphene sheets according to various aspects of the subject matter disclosed herein can provide natural evolution in the direction of enhanced energy storage density.

將個別石墨烯片作為電漿生長過程之一部分保持在適當位置。如先前來自FLG及/或用以形成粒子諸如，以碳為主之粒子100A、100E、402A及/或其類似物)之組合所描述，以碳為主之球狀(gumball-like)結構以經界定長程次序正在運行地自裝配，其界定為其中固體碳材料展現出結晶相結構。一旦界定碳原子及其相鄰者之位置，則可在整個結晶相結構中精確界定每一碳原子之位置以使得較小結構黏聚，以形成基本上類似於球之結構。Keep individual graphene sheets in place as part of the plasma growth process. As previously described from the combination of FLG and/or used to form particles such as carbon-based particles 100A, 100E, 402A and/or the like, the carbon-based gumball-like structure is The defined long-range sequence is running self-assembly, which is defined as where the solid carbon material exhibits a crystalline phase structure. Once the positions of the carbon atoms and their neighbors are defined, the position of each carbon atom can be precisely defined in the entire crystalline phase structure to make smaller structures agglomerate to form a structure that is substantially similar to a sphere.

描述個別以碳為主之粒子100A及/或其類似者的此類球狀結構之尺寸維度在其各別最寬點上可為約100 nm。形成如圖18中所示之碳晶格結構1800的較大黏聚粒子可由多個球狀結構組成，直徑可為較大數量級，約20微米至30微米，且為圖4A中所示之膜層406A至412A中之一或多者提供結構界定。The size dimension of such spherical structures describing individual carbon-based particles 100A and/or the like can be about 100 nm at their respective widest points. The larger cohesive particles forming the carbon lattice structure 1800 as shown in FIG. 18 can be composed of multiple spherical structures, and the diameter can be a larger order of magnitude, about 20 to 30 microns, and is the film shown in FIG. 4A One or more of layers 406A to 412A provide structural definition.

對比而言，傳統的電池電極產生方法通常使用已知沈積技術(諸如化學氣相沈積(CVD)或其他製造技術、奈米管等)以使結構離開界定的固定基體或表面生長，且因此不涉及本文所揭露之含碳氣態物質之實質上大氣蒸氣流物料流中之以碳為主之粒子之正在運行的熔合。此類已知裝配過程及程序可能往往為極勞力密集的，且其亦可允許生長厚度有限(200微米至300微米厚)之結構。In contrast, traditional battery electrode production methods usually use known deposition techniques (such as chemical vapor deposition (CVD) or other manufacturing techniques, nanotubes, etc.) to make the structure grow away from the defined fixed substrate or surface, and therefore does not It involves the running fusion of carbon-based particles in the substantially atmospheric vapor stream of the carbon-containing gaseous material disclosed herein. Such known assembly processes and procedures may often be extremely labor-intensive, and they may also allow the growth of structures with a limited thickness (200 microns to 300 microns thick).

諸如以碳為主之粒子100A、碳支架300B、鋰化碳支架400A及/或其類似者的多個FLG在原始球狀碳支架上之石墨烯與石墨烯的緻密化亦可使得能量密度及容量增大。亦可在產生包含多個以碳為主之粒子100A的較大黏聚粒子之後執行或以其他方式實現碳支架之目標區域中的此類緻密化。一般而言，可在還原之前將Li離子電鍍至電極上，因此視電池化學性質而定，Li離子可自離子過渡至金屬狀態。此外，在一實施方案中，類似於電鍍，石墨烯可以堆疊方式生長於諸如塑膠之其他材料上，且經調諧以得到合乎需要的明亮及/或光滑修整面層。此類電鍍過程為可逆的且可包含單獨但相關的鍍覆過程及剝離過程，該等剝離過程意欲將Li離子及/或原子向下置放且用於其後續移除。The densification of graphene and graphene of multiple FLGs such as carbon-based particles 100A, carbon scaffold 300B, lithiated carbon scaffold 400A, and/or the like on the original spherical carbon scaffold can also make the energy density and Increased capacity. This type of densification in the target area of the carbon scaffold can also be performed after generating larger cohesive particles including a plurality of carbon-based particles 100A or in other ways. Generally speaking, Li ions can be electroplated onto the electrode before reduction. Therefore, depending on the battery chemistry, Li ions can transition from ion to metallic state. In addition, in one embodiment, similar to electroplating, graphene can be grown on other materials such as plastic in a stacked manner, and tuned to obtain a desired bright and/or smooth finish. Such electroplating processes are reversible and may include separate but related plating processes and stripping processes, which are intended to place Li ions and/or atoms downward and for their subsequent removal.

在涉及多個充電-放電-再充電之循環之二次Li離子電池的持續不斷循環使用中，以碳為主之結構生長及/或構建之表面最終變得粗糙且因此對不合需要之樹枝狀結晶生長敏感或阻止不合需要之樹枝狀結晶生長。對比而言，如上文所論述，用以產生以碳為主之粒子100A及/或其類似者的技術藉由使用實質上不含雜質之Li金屬連同以碳為主之石墨烯結構而能夠達到較高比容量值，從而能夠實質上防止此類樹枝狀結晶生長。In the continuous recycling of secondary Li-ion batteries involving multiple charge-discharge-recharge cycles, the surface of carbon-based structure growth and/or construction will eventually become rough and therefore undesirable dendritic Crystal growth is sensitive or prevents undesirable dendritic crystal growth. In contrast, as discussed above, the technology for producing carbon-based particles 100A and/or the like can be achieved by using Li metal that is substantially free of impurities together with a carbon-based graphene structure. A higher specific capacity value can substantially prevent the growth of such dendrites.

使用石墨烯片准許相對較大之暴露表面積，其可用於鍍覆或間夾操作以用於涉及Li離子之非反應性毛細管灌注之浸潤。因此，消除移動至某一點之任何傾向；且基本上，歸因於石墨烯與諸如石墨之其他習知以碳為主之材料相比具有較高表面積與體積比，可改變發生鍍覆及剝離方式。可至少部分地依賴於液體Li來引入Li離子；然而，鑒於Li易於與周圍及/或周圍元素之化學反應性，必須遠離水類濕氣及氧氣。類似地，引入雜質產生有害作用。關於所揭露之以碳為主之結構，已研究金屬-基質複合物(關於Li金屬化鍵結或以其他方式與C形成金屬-基質複合物)，因此提供關於暴露表面處反應性之可精細調諧性及管理之額外選擇。The use of graphene sheets permits a relatively large exposed surface area, which can be used for plating or sandwiching operations for the infiltration of non-reactive capillary perfusion involving Li ions. Therefore, any tendency to move to a certain point is eliminated; and basically, due to the fact that graphene has a higher surface area to volume ratio than other conventional carbon-based materials such as graphite, which can change the occurrence of plating and peeling Way. The introduction of Li ions may be at least partially dependent on liquid Li; however, in view of Li's easy chemical reactivity with surrounding and/or surrounding elements, it must be kept away from water-like moisture and oxygen. Similarly, the introduction of impurities produces harmful effects. Regarding the disclosed carbon-based structure, metal-matrix composites (about Li metallization bonding or other forms of metal-matrix composites with C in other ways) have been studied, and therefore provide a finer measure of the reactivity at the exposed surface Additional options for tuning and management.

與C接觸之Li可導致在接觸表面處的Li之自由能必須受到抑制及/或控制，以避免與以碳為主之粒子100A及/或其類似者中之自發性Li浸潤相關的非所需反應性之情形。傳統地，歸因於電解質之化學性質，液相中之Li通常形成碳酸鹽及其他形成物。然而，本發明實例所提出的係關於在引入液體電解質之前產生相對穩定之固體電解質界面(SEI)。Li in contact with C may cause the free energy of Li at the contact surface to be suppressed and/or controlled to avoid inconsistencies related to spontaneous Li infiltration in carbon-based particles 100A and/or the like Circumstances that require reactivity. Traditionally, due to the chemical properties of the electrolyte, Li in the liquid phase usually forms carbonates and other formations. However, what the example of the present invention proposes is to create a relatively stable solid electrolyte interface (SEI) before introducing the liquid electrolyte.

此外，影響Li離子界面區域之多種方法及/或過程可為可用的。舉例而言，藉由與Si及其他元素合金化來製備液體Li的表面將降低反應性且促進較大黏聚粒子的總體Li離子潤濕，該等較大黏聚粒子各自包括多個以碳為主之粒子100A。在一實例中，觀測到約小於1.5%之Li優先移動至暴露於電解質之暴露表面。 相較於習知石墨陽極 ， 比容量增加 ( 約3 倍 ) 之3D 階層式石墨烯 In addition, various methods and/or processes that affect the Li ion interface region may be available. For example, preparing the surface of liquid Li by alloying with Si and other elements will reduce the reactivity and promote the overall Li ion wetting of larger cohesive particles, each of which includes a plurality of carbon-based particles. The main particle is 100A. In one example, it was observed that less than 1.5% of Li preferentially moved to the exposed surface exposed to the electrolyte. Compared with conventional graphite anodes , 3D hierarchical graphene with increased specific capacity ( about 3 times )

用於陽極活性材料之石墨碳材料以及用於電傳導之細碳黑材料的商業用途因其具有相對較低成本、用於***及提取Li+離子之極佳結構完整性、與Li樹枝狀結晶形成無關之安全性及針對許多電解質之保護鈍化層的形成而為合理的，該等電解質諸如與固體電解質相間(SEI)之形成或積聚相關聯之電解質。The commercial use of graphite carbon materials for anode active materials and fine carbon black materials for electrical conduction is due to their relatively low cost, excellent structural integrity for insertion and extraction of Li+ ions, and formation of Li dendrites The irrelevant safety and the formation of a protective passivation layer for many electrolytes, such as those associated with the formation or accumulation of solid electrolyte interphase (SEI), are reasonable.

然而，在372 mAh/g下具有化學計量式LiC₆ 的石墨之較低比容量為一種關鍵限制，且因此可潛在地妨礙需要高能量及功率密度之大規模能量儲存系統的發展。藉由設計及應用如本文藉由前述圖中之任一者或多者所揭露之間夾有Li及/或S之化合物電極方法的三維(3D)石墨烯，可調節較大負載量之活性陽極材料，同時促進Li離子擴散。此外，諸如由開放多孔支架102A及/或其類似物界定之3D奈米碳構架可賦予： ●            導電路徑；及 ●            用以較高容量非碳奈米材料的結構緩衝器，其產生增強的Li離子儲存容量。 (1)及(2)二者增強Li離子儲存容量(＞1,000 mAh/g)且增強的循環(穩定性)效能可使用此等3D結構達成。 與 Li 離子 ( 及 Li S ) 電池電極之整合 _{However, the lower specific capacity of graphite with stoichiometric LiC 6} at 372 mAh/g is a key limitation, and therefore may potentially hinder the development of large-scale energy storage systems that require high energy and power density. By designing and applying three-dimensional (3D) graphene as disclosed in any one or more of the foregoing figures in the compound electrode method with Li and/or S in between, the activity of a larger load can be adjusted Anode material, while promoting the diffusion of Li ions. In addition, a 3D nano-carbon framework such as defined by the open porous scaffold 102A and/or the like can give: ● conductive paths; and ● a structural buffer for higher capacity non-carbon nanomaterials, which produces enhanced Li Ion storage capacity. Both (1) and (2) enhance Li ion storage capacity (>1,000 mAh/g) and enhanced cycle (stability) performance can be achieved using these 3D structures. Integration with Li ion ( and Li S ) battery electrodes

圖5顯示例示性Li離子或Li S二次電化電池系統500，其具有由隔板517分隔之陽極501及陰極502。陽極501及陰極502中之任一者或多者可實質上由圖4A中所示之鋰化碳支架400A形成，且在此處以較大及較小碳粒子509之簡化表示來表示，所有該等碳粒子均至少部分地限制含有如所示之解離Li離子傳導鹽505的Li離子傳導電解質溶液518。隔板(將陽極501及陰極502彼此電隔離之多孔膜)亦位於所示位置。單一Li離子在放電-充電循環期間經由路徑507來回遷移於Li離子電池之電極之間，且間夾至以碳為主之活性材料中，形成陽極501及陰極502中之任一者或多者，視需要限制於其中，得到最佳二次電化電池500效能。FIG. 5 shows an exemplary Li ion or Li S secondary electrochemical battery system 500, which has an anode 501 and a cathode 502 separated by a separator 517. Any one or more of the anode 501 and the cathode 502 can be substantially formed of the lithiated carbon support 400A shown in FIG. 4A, and is represented here by a simplified representation of larger and smaller carbon particles 509, all The carbon particles are at least partially confined to the Li ion conductive electrolyte solution 518 containing the dissociated Li ion conductive salt 505 as shown. The separator (the porous membrane that electrically isolates the anode 501 and the cathode 502 from each other) is also located at the position shown. A single Li ion migrates back and forth between the electrodes of the Li-ion battery via the path 507 during the discharge-charge cycle, and is sandwiched between the carbon-based active material to form any one or more of the anode 501 and the cathode 502 , Limited to them as needed, to get the best performance of the secondary electrochemical battery 500.

諸如電解質溶液518之電解質可一般分成若干廣泛類別，包括液體電解質及固體電解質。液體電解質歸因於電極內之其較高離子傳導性、較低表面張力、較低界面阻抗及良好可濕性而作為許多習知電池組之最常用電解質系統。在Li S電池系統中，液體電解質占主導，此係因為其幫助補償大量潛在遇到的S及鋰硫化物(Li₂ S)之不良電化動力學。在Li S系統中，可使用含有以醚為主之溶劑的液體電解質，此係因為不同於碳酸酯，以醚為主之溶劑並不與S不利地反應且一般具有較佳Li離子運輸特性。使用以醚為主之電解質的潛在缺點包括長鏈聚硫化物(PS)之可溶性，其可歸因於PS穿梭、電子遷移及陰極之體積膨脹而最終導致Li S電化電池降解，從而損害其結構完整性。Electrolytes such as electrolyte solution 518 can generally be divided into several broad categories, including liquid electrolytes and solid electrolytes. Liquid electrolyte is the most commonly used electrolyte system in many conventional battery packs due to its higher ion conductivity, lower surface tension, lower interface resistance and good wettability in the electrode. In Li S battery systems, liquid electrolytes dominate because they help compensate for the large amounts of potentially encountered S and the poor electrochemical kinetics of _{lithium sulfide (Li 2 S).} In the Li S system, liquid electrolytes containing ether-based solvents can be used. This is because unlike carbonates, ether-based solvents do not adversely react with S and generally have better Li ion transport characteristics. The potential disadvantages of using ether-based electrolytes include the solubility of long-chain polysulfide (PS), which can be attributed to PS shuttle, electron migration, and volume expansion of the cathode, which ultimately leads to degradation of the Li S electrochemical cell, thereby damaging its structure Completeness.

在習知液相電解質外部，固態電解質可潛在地經組配以停止Li樹枝狀結晶之形成及生長，且在固態電解質將Li S系統自多相系統有效地轉換為單相位系統時停止PS穿梭，從而不會引起內部短路、電解質洩漏及非可燃性。固體聚合物電解質可界定為具有在膜上輸送Li離子之能力的多孔膜。固體電解質可進一步分類成固體聚合物電解質、凝膠聚合物電解質及非聚合物電解質。固體聚合物電解質可由溶解於高分子量聚合物主體中之鋰鹽構成。所使用之常見聚合物主體為聚乙二醇(PEO)、聚偏二氟乙烯或聚偏二氟乙烯(PVDF)、聚(氧化對伸苯基)或聚(PPO)、聚(偏二氟乙烯-共聚-六氟丙烯) (PVDF-HFP)及聚(甲基丙烯酸甲酯) (PMMA)等。Outside of the conventional liquid electrolyte, the solid electrolyte can potentially be configured to stop the formation and growth of Li dendrites, and stop PS when the solid electrolyte effectively converts the Li S system from a multiphase system to a single phase system. Shuttle, so as not to cause internal short circuit, electrolyte leakage and non-flammability. The solid polymer electrolyte can be defined as a porous membrane that has the ability to transport Li ions on the membrane. Solid electrolytes can be further classified into solid polymer electrolytes, gel polymer electrolytes, and non-polymer electrolytes. The solid polymer electrolyte can be composed of a lithium salt dissolved in a high molecular weight polymer body. The common polymer main body used is polyethylene glycol (PEO), polyvinylidene fluoride or polyvinylidene fluoride (PVDF), poly(paraphenylene oxide) or poly(PPO), poly(vinylidene fluoride) Ethylene-co-hexafluoropropylene) (PVDF-HFP) and poly(methyl methacrylate) (PMMA), etc.

凝膠聚合物電解質可類似於固體聚合物電解質，因為其具有較高分子量聚合物，且亦包括緊緊地捕獲於聚合物基質內之液體組分。在一些實施方案中，發展凝膠聚合物電解質以補償在固體聚合物電解質中觀測到的不良離子傳導性。優於固體電解質之其他形式，非聚合物固體電解質具有較高熱穩定性及化學穩定性之優點。A gel polymer electrolyte can be similar to a solid polymer electrolyte because it has a higher molecular weight polymer and also includes a liquid component tightly trapped within a polymer matrix. In some embodiments, gel polymer electrolytes are developed to compensate for the poor ionic conductivity observed in solid polymer electrolytes. Better than other forms of solid electrolytes, non-polymer solid electrolytes have the advantages of higher thermal stability and chemical stability.

非聚合物固體電解質由陶瓷組成且通常發現之非聚合物電解質包括超離子導體(LISICON)、Li₇ La₃ Zr₂ O₁₂ (LLZO)、Li₇ La_2.75 Ca_0.25 Zr_1.75 Nb_0.25 O₁₂ (LLCZN)、Garnet及摻雜Ge之Li_0.33 La_0.56 TiO₃ (Ge-LLTO)鈣鈦礦等，且厚度可在約0.5 μM至40 μM之範圍內，其可經組配以實質上防止Li樹枝狀結晶形成或生長中之任一者或多者。儘管如此，一些固體電解質仍可能具有某些難題，包括相對不良的Li離子傳導性及重量。在防止Li樹枝狀結晶生長所需之厚度下，所觀測到的離子阻抗可能非常高，以使得如此裝備的Li離子或Li S電池可能無法按要求起作用，而在需要具有可接受Li離子傳導率之厚度下，可能不會避免Li樹枝狀結晶生長。Non-polymer solid electrolytes are composed of ceramics and commonly found non-polymer electrolytes include super ionic conductors (LISICON), Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO), Li ₇ La _2.75 Ca _0.25 Zr _1.75 Nb _0.25 O ₁₂ (LLCZN ), Garnet and Ge-doped Li _0.33 La _0.56 TiO ₃ (Ge-LLTO) perovskite, etc., and the thickness can be in the range of about 0.5 μM to 40 μM, which can be combined to substantially prevent Li dendrites Either or more of crystal formation or growth. Nevertheless, some solid electrolytes may still have certain problems, including relatively poor Li ion conductivity and weight. Under the thickness required to prevent the growth of Li dendrites, the observed ion resistance may be very high, so that the Li ion or Li S battery equipped in this way may not function as required, and it is necessary to have acceptable Li ion conduction. Under the thickness of the rate, the growth of Li dendritic crystals may not be avoided.

在放電期間，Li自陽極501去間夾。陰極502之活性材料可包括混合氧化物。陽極501之活性材料可主要包括石墨及非晶碳化合物，包括本文所呈現之彼等化合物。此等材料為間夾有Li之材料。During the discharge, Li is removed from the anode 501. The active material of the cathode 502 may include a mixed oxide. The active material of the anode 501 may mainly include graphite and amorphous carbon compounds, including those compounds presented herein. These materials are materials with Li interposed therebetween.

Li離子傳導鹽505可解離以提供可間夾至本文所揭露之獨特的以碳為主之結構中的任一者或多者中的可移動Li離子，該等Li離子可併入至陽極501或陰極502中之任一者或多者中作為結構材料以達成超過1,100 mAh/g或更高的比容量保持能力，如藉由相連微結構107F促進。Li離子與Li S系統中之S形成複合物及/或化合物，且在充電-放電循環期間暫時限制於習知未組織碳結構不可另外達成之位準下(需要經由黏著力定義及組合)，其亦可抑制總電池效能及耐久性，如早先所論述。The Li ion conductive salt 505 can be dissociated to provide mobile Li ions that can be sandwiched between any one or more of the unique carbon-based structures disclosed herein, and these Li ions can be incorporated into the anode 501 Or any one or more of the cathode 502 is used as a structural material to achieve a specific capacity retention capacity exceeding 1,100 mAh/g or higher, as promoted by the connected microstructure 107F. Li ions form complexes and/or compounds with S in the Li S system, and are temporarily restricted to a level that cannot be otherwise achieved with conventional unorganized carbon structures during the charge-discharge cycle (need to be defined and combined through adhesion), It can also suppress overall battery performance and durability, as discussed earlier.

圖1F所示之相連微結構107F之孔隙105F，其可形成以碳為主之粒子100A、100E、402A及/或其類似物且用於產生陽極501或陰極502中之任一者或多者的傳導性分級膜層，其可在合成期間經界定以包括微孔隙體積(孔隙＜1.5 nm)。經由毛細管力將硫(S)灌注至孔隙105F中，其中S被限制。硫之成功微米限制將防止溶解之聚硫化物(PS) (如較早關於Li S系統所呈現)一般再沈澱至其原始孔隙外部。為達成能夠保持可達成數量之S的活性碳複合物，可需要1.7 cc/g之孔隙體積，所有1.7 cc/g使得孔隙之開口為＜1.5 nm。The pore 105F of the connected microstructure 107F shown in FIG. 1F can form carbon-based particles 100A, 100E, 402A and/or the like and used to produce any one or more of the anode 501 or the cathode 502 A conductive graded membrane layer of, which can be defined during synthesis to include micropore volume (pores <1.5 nm). Sulfur (S) is injected into the pore 105F via capillary force, where S is restricted. The successful micro-limitation of sulfur will prevent the dissolved polysulfide (PS) (as presented earlier for the Li S system) from generally re-precipitating outside of its original pores. In order to achieve an activated carbon composite that can maintain an achievable amount of S, a pore volume of 1.7 cc/g may be required, and all 1.7 cc/g makes the pore opening less than 1.5 nm.

操作上，在Li離子或Li S系統中，Li離子自陽極501經由電解質518及隔板517遷移至陰極502。此處，如放大區域516及513中所示，熔融Li金屬514微米限制在與用作陽極501或陰極502之結構的本發明所揭露之以碳為主之結構中之任一者相關聯的少層石墨烯片515內。熔融Li金屬可依照以下方程式(8)在陽極501中解離： (8)   FLG-Li

FLG + Li+ e-In operation, in a Li ion or Li S system, Li ions migrate from the anode 501 to the cathode 502 via the electrolyte 518 and the separator 517. Here, as shown in the enlarged regions 516 and 513, the molten Li metal 514 microns is restricted to any one of the carbon-based structures disclosed in the present invention used as the structure of the anode 501 or the cathode 502 Few layers of graphene sheet 515 inside. The molten Li metal can be dissociated in the anode 501 according to the following equation (8): (8) FLG-Li

FLG + Li+ e-

方程式(1)顯示電子506及511放電508以向外部負載供電，使得遷移至陰極502之Li離子512依照以下方程式(9)返回至以氧化鈷為主之晶格內的熱力學上有利之位置： (9)  xLi⁺ + xe^- +Li_1-x CoO₂

LiCoO₂ 。 在充電期間，此過程相反，其中Li離子505自陰極502經由電解質518及隔板517轉移至陽極501。Equation (1) shows that the electrons 506 and 511 discharge 508 to supply power to the external load, so that the Li ions 512 migrated to the cathode 502 return to a thermodynamically favorable position in the cobalt oxide-based lattice according to the following equation (9): ^{(9) xLi + + xe -} + Li 1-x CoO 2

LiCoO ₂ . During charging, the process is reversed, in which Li ions 505 are transferred from the cathode 502 to the anode 501 via the electrolyte 518 and the separator 517.

所揭露之以碳為主之結構，參看藉由以碳為主之粒子100A、100E及/或其衍生物(包括碳支架300B及鋰化碳支架400A)之獨特多模態階層式結構而製造的出人意料的有利的比容量值，該等結構中之任一者或多者可經組配以產生由Li離子技術提供之傳統優點。與鈉離子或鉀離子相比，相對較小Li離子在不同氧化陰極材料中展現出顯著較快動力學。另一差異包括與其他鹼金屬相反，Li離子可逆地間夾及去間夾於石墨及矽(Si)中。且鋰化石墨電極致能較高電池電壓。因此，由於少層石墨烯(FLG) (諸如呈一般水平堆疊組配101C之5至15層石墨烯)之獨特疊層，所揭露之以碳為主之材料增強Li離子可逆地間夾及去間夾於石墨烯片之間的簡易性，如在以碳為主之粒子100A及/或其類似物中所採用，且適合於應用硬殼、袋式電池及稜鏡應用。 藉由摻雜使人造固體 與 電解質界面 ( SEI ) 膜穩定化 The disclosed carbon-based structure, please refer to the unique multi-modal hierarchical structure manufactured by carbon-based particles 100A, 100E and/or their derivatives (including carbon support 300B and lithiated carbon support 400A) With the unexpectedly favorable specific capacity values, any one or more of these structures can be combined to produce the traditional advantages provided by Li-ion technology. Compared with sodium ions or potassium ions, relatively small Li ions exhibit significantly faster kinetics in different oxidation cathode materials. Another difference includes that in contrast to other alkali metals, Li ions are reversibly sandwiched between graphite and silicon (Si). And the lithiated graphite electrode enables higher battery voltage. Therefore, due to the unique stack of few-layer graphene (FLG) (such as 5 to 15 layers of graphene in a general horizontal stacking configuration 101C), the disclosed carbon-based materials enhance the reversible intercalation and removal of Li ions. The ease of sandwiching between graphene sheets, such as used in carbon-based particles 100A and/or the like, is suitable for hard case, pouch type batteries, and high-end applications. By doping with artificial solid electrolyte interface (SEI) film is stabilized

目前，當首先引入電解液接著進行初始放電及充電步驟時，當前Li離子電池在預調節步驟期間在暴露於電解液之電極表面處形成保護性鈍化層(諸如圖4A中所示之鈍化層418A)或固體電解質界面(SEI)。儘管可調節諸如充電/放電速率及過電壓之電解質化學及預處理方案以使膜鈍化最佳化，參看SEI形成，併入至電極中之習知膜層仍可具有化學及機械方式不穩定性。At present, when the electrolyte is first introduced and then the initial discharging and charging steps are performed, the current Li-ion battery forms a protective passivation layer (such as the passivation layer 418A shown in FIG. 4A) at the electrode surface exposed to the electrolyte during the preconditioning step. ) Or solid electrolyte interface (SEI). Although the electrolyte chemistry and pretreatment schemes such as charge/discharge rate and overvoltage can be adjusted to optimize film passivation, see SEI formation, the conventional film layer incorporated into the electrode can still have chemical and mechanical instability .

現參看圖6A，可藉由摻雜將特定元素602A引入至前述碳材料600A。可將實例暴露電極表面601A處諸如矽、硫、氮、磷之元素602A以規定位準之等形覆蓋塗佈至碳結構之電極表面601A上，諸如疏鬆裝飾至完全等形覆蓋。文獻中已報導優先形成穩定的固態電解質離子傳導層；參見以硫為主之thioLISCON，其定義為具有化學式Li_3.25 Ge_0.25 P_0.75 S₄ 之鋰硫導體及以磷酸根為主之NASCION，諸如鈉(Na)超離子導體，其通常係指具有化學式Na_1+x Zr₂ Si_x P_{3 −x} O₁₂ (0＜x＜3)之固體家族，且縮寫字亦用於類似化合物，其中Na、Zr及/或Si經同價元素置換。如此處所解釋，穩定的固態鈍化層之形成包括摻雜特定元素602A，電極表面601A可在電池裝配之前經工程改造，從而使穩定固態離子傳導層之形成過程與當與電解質接觸時所發生之還原/氧化事件去耦，如當前Li離子電池製造中所遇到，其仍常常遭受長期穩定的操作。 使用漿料澆鑄技術之製造 Referring now to FIG. 6A, a specific element 602A can be introduced into the aforementioned carbon material 600A by doping. The elements 602A such as silicon, sulfur, nitrogen, and phosphorous at the exposed electrode surface 601A can be coated on the electrode surface 601A of the carbon structure at a predetermined level, such as loose decoration to complete contour coverage. It has been reported in the literature to preferentially form a stable solid electrolyte ion conductive layer; see sulfur-based thioLISCON, which is defined as a _{lithium-sulfur conductor with the chemical formula Li 3.25} Ge _0.25 P _0.75 S ₄ and a phosphate-based NASCION, such as sodium (Na) Superionic conductor, which usually refers to _{the solid family with the chemical formula Na 1+x} Zr ₂ Si _x P _{3 −x} O ₁₂ (0＜x＜3), and the abbreviations are also used in similar compounds, among which Na, Zr and/or Si are replaced with elements of the same valence. As explained here, the formation of a stable solid-state passivation layer includes doping with specific elements 602A. The electrode surface 601A can be engineered before the battery is assembled, so that the formation of the stable solid-state ion conductive layer and the reduction that occurs when in contact with the electrolyte /Oxidation event decoupling, as encountered in current Li-ion battery manufacturing, it still often suffers from long-term stable operation. Manufacturing using slurry casting technology

與諸如碳黑之傳導性粒子及任擇聚合物黏合劑及諸如NMP之溶劑組合，本文所揭露之經調諧3D階層式以石墨烯為主之粒子中之任一者或多者可直接併入至如下的習知漿料鑄造電極製造過程中： ●            在陽極之情況下以活性石墨烯為主(FLG)取代石墨粒子；及/或 ●            在陰極之情況下用活性硫(S)灌注。 3D石墨烯粒子為較高比容量石墨烯構建區塊提供用於快速Li離子運輸之互連的中孔離子傳導通道以及碳黑及黏合劑，以確保導電路徑，諸如用作連續微結構107F之結構材料的石墨烯片101B所界定，其亦提供機械完整性。In combination with conductive particles such as carbon black, optional polymer binders, and solvents such as NMP, any one or more of the tuned 3D hierarchical graphene-based particles disclosed herein can be directly incorporated To the following conventional slurry casting electrode manufacturing process: ● In the case of anode, use active graphene (FLG) to replace graphite particles; and/or ● In the case of the cathode, it is filled with active sulfur (S). 3D graphene particles provide high specific capacity graphene building blocks with interconnected mesoporous ion conduction channels for rapid Li ion transport, as well as carbon black and binders to ensure a conductive path, such as the continuous microstructure of 107F The structure material is defined by the graphene sheet 101B, which also provides mechanical integrity.

所揭露之碳材料可藉由球磨研磨及/或熱退火後及來自第三電極之電化還原來預鋰化，其以： ●            相對較低濃度以抵消習知氧化陰極電池之第一電荷Li損失；或 ●            相對較高濃度以增加氧化及替代性陰極組配二者之總比容量，且隨後將漿料澆鑄至電極中。The disclosed carbon material can be pre-lithiated by ball milling and/or thermal annealing and electrochemical reduction from the third electrode, which is: ● Relatively low concentration to offset the first charge Li loss of conventional oxide cathode batteries; or ● Relatively high concentration to increase the total specific capacity of oxidation and alternative cathode assembly, and then the slurry is poured into the electrode.

圖6B1及圖6B2顯示根據一些實施方案之在活性材料浸潤及活性材料內之鋰(Li)限制的情形下將化學非反應性系統600B1與化學反應性系統600B2進行比較的示意圖。儘管熔融Li金屬浸潤至圖1A至圖1F中所示之本發明所揭露的以碳為主之結構(諸如相連微結構107F)之任一者或多者的組配，替代或額外實施方案提供在氣相中將熔融的Li金屬液滴灌注至孔隙，諸如孔隙105F中。在化學非反應性系統600B1中，製備Li金屬液滴，或預期Li金屬液滴在與暴露碳表面接觸時未能與碳反應，此係由於例如碳之Li疏水性。無論如何，以約50°與90°之間的內部接觸角(θ)灌注蒸氣相Li液滴可提供競爭性液體與固體黏著力之間的平衡，諸如在液相熔融Li液滴與固相碳(γ_sl )之間觀測到的黏著力，該固相碳與液體中之(γ_lv )黏合力成比例。6B1 and 6B2 show schematic diagrams comparing the chemically non-reactive system 600B1 with the chemically reactive system 600B2 in the case of active material infiltration and lithium (Li) limitation in the active material according to some embodiments. Although the molten Li metal infiltrates into the combination of any one or more of the carbon-based structures (such as the connected microstructure 107F) disclosed in the present invention shown in FIGS. 1A to 1F, alternative or additional embodiments are provided The molten Li metal droplets are poured into the pores, such as the pore 105F, in the gas phase. In the chemically non-reactive system 600B1, Li metal droplets are prepared, or the Li metal droplets are expected to fail to react with carbon when in contact with exposed carbon surfaces, due to, for example, the Li hydrophobicity of carbon. In any case, infusing vapor phase Li droplets with an internal contact angle (θ) between about 50° and 90° can provide a balance between competitive liquid and solid adhesion, such as melting Li droplets and solid phases in the liquid phase. The observed adhesion between carbon (γ _sl ), the solid phase carbon is proportional to the (γ _lv ) adhesion in the liquid.

將氣相Li與固相碳之間發生的潤濕界定為液體維持與固體表面接觸之能力，其由二者接觸在一起時由分子間相互作用產生，其中潤濕程度或可濕性可由黏著力與黏合力之間的力平衡確定。所需潤濕程度可出現在以下情況下：黏著能量接近黏性能量，諸如具有緊緊固持的鍵，如在分散於固相金屬上之液相金屬中，或在包括矽(Si)、鍺(Ge)或碳化矽(SiC)之半導體中所見，以及包括碳化物、氮化物或硼化物中之任一者或多者的陶瓷，其可展現出接近暴露表面之金屬類特性。且使用對諸如氧(O)、氮(N)或濕氣(H₂ O蒸氣)或碳之大氣污染物具有相對較高可溶性之液相金屬可降低在受污染固體表面處或在純碳表面處潤濕期間所觀測或所需之接觸角。The wetting between Li and solid carbon in the gas phase is defined as the ability of the liquid to maintain contact with the solid surface, which is produced by the intermolecular interaction when the two are in contact. The force balance between force and adhesion force is determined. The required degree of wetting can occur in the following situations: the adhesion energy is close to the viscous energy, such as with tightly held bonds, such as in the liquid metal dispersed on the solid phase metal, or in the case of silicon (Si), It is found in germanium (Ge) or silicon carbide (SiC) semiconductors, and ceramics including any one or more of carbides, nitrides, or borides, which can exhibit metallic characteristics close to the exposed surface. And the use of liquid metal with relatively high solubility to atmospheric pollutants such as oxygen (O), nitrogen (N) or moisture (H ₂ O vapor) or carbon can reduce the concentration on the contaminated solid surface or on the surface of pure carbon. The contact angle observed or required during the wetting period.

在化學反應性系統600B2中，諸如在暴露於Li金屬之以碳為主之粒子100A之表面上的碳表面層602B2之潤濕可伴隨有在彼界面處發生之化學反應，諸如溶解固體碳材料或形成新3D層604B2或涉及底層碳表面層604B2之至少部分消耗的化合物。在碳表面層602B2處添加藉由類型及濃度調諧之摻雜物亦可影響潤濕程度，如藉由各種流體位置606B2、608B2及610B2所示，顯示在位置606B2處具有極小潤濕且分別在位置608B2及610B2處具有逐漸較大潤濕之熔融Li液滴。在一些實施方案中，新3D層604B2之形成可改變底層碳表面層602B2之特性，該等特性包括電導率，或可以其他方式(藉由夾斷)限制藉由形成體積膨脹之反應產物(顯示為新3D層604B2)而浸潤至多孔介質中。In the chemically reactive system 600B2, for example, the wetting of the carbon surface layer 602B2 on the surface of the carbon-based particles 100A exposed to Li metal may be accompanied by chemical reactions occurring at the interface, such as dissolving solid carbon materials Or the formation of a new 3D layer 604B2 or at least a partially consumed compound involving the underlying carbon surface layer 604B2. Adding dopants adjusted by type and concentration at the carbon surface layer 602B2 can also affect the degree of wetting. Positions 608B2 and 610B2 have gradually larger wetted molten Li droplets. In some embodiments, the formation of the new 3D layer 604B2 can change the characteristics of the underlying carbon surface layer 602B2, which include electrical conductivity, or can be restricted by other means (by pinch-off) by forming volume expansion reaction products (showing Infiltrate into the porous medium for the new 3D layer 604B2).

對於化學非反應性系統600B1或化學反應性系統600B2，減小液體Li金屬液滴珠粒(諸如位置610B2中所示液滴珠粒)之接觸角可促進底層碳表面層602B2之潤濕。且對於碳表面層602B2併有吸附或化學鍵結之氧(O)的組配，添加具有較高O可溶性之元素(諸如亦被稱作收氣劑)可降低或以其他方式控制新3D層604B2處之O活性。對於碳表面層602B2之固體變體，向具有較高碳可溶性之液相金屬添加諸如鎳(Ni)、鐵(Fe)或其他元素可確保相對較高之表面活性或親和力。For the chemically non-reactive system 600B1 or the chemically reactive system 600B2, reducing the contact angle of the liquid Li metal droplet beads (such as the droplet beads shown in position 610B2) can promote the wetting of the bottom carbon surface layer 602B2. And for the combination of carbon surface layer 602B2 with adsorbed or chemically bonded oxygen (O), adding elements with higher O solubility (such as also called getters) can reduce or otherwise control the new 3D layer 604B2 O activity at the place. For the solid variant of the carbon surface layer 602B2, adding nickel (Ni), iron (Fe) or other elements to the liquid metal with higher carbon solubility can ensure relatively higher surface activity or affinity.

圖7顯示根據一些實施方案之實例過程工作流程，其中將熔融Li金屬浸潤至碳黏聚體之間的空隙空間中以引發暴露碳表面處之反應。將Li金屬704、706浸潤至封裝碳支架702中之考慮顯示於浸潤過程工作流程示意圖700中，該等考慮可併入本文所揭露之以碳為主之結構中之任一者或多者(諸如圖1A中所示之碳粒子100A或圖1F中所示之相連微結構107F)內或另外提供該等結構材料。可在藉由熔融Li金屬浸潤之前調諧碳支架702之表面條件，熔融Li金屬可藉由使用液相中之熔融Li金屬之毛細管灌注或懸浮於空氣中之熔融Li金屬液滴之灌注中之任一者或多者進入碳支架702中，從而形成Li金屬蒸氣。精確調諧在暴露於進入之Li之碳支架702表面處的以下條件，包括控制： ●      大氣污染物，諸如濕氣(H₂ O蒸氣)、氧氣(O)、氮氣(N)及經組配以限制或含有生理吸附或化學吸附型O之烴； ●            在電漿後處理期間在表面上形成氮鍵；及 ●            Li金屬之純度，諸如控制普遍的表面氧化物、氮化物及碳酸鹽。Figure 7 shows an example process workflow according to some embodiments, in which molten Li metal is infiltrated into the void spaces between carbon cohesives to initiate a reaction at the exposed carbon surface. The considerations for infiltration of Li metals 704 and 706 into the packaged carbon support 702 are shown in the infiltration process workflow diagram 700. These considerations can be incorporated into any one or more of the carbon-based structures disclosed herein ( Such structural materials may be provided in the carbon particles 100A shown in FIG. 1A or the connected microstructures 107F shown in FIG. 1F) or in addition. The surface condition of the carbon stent 702 can be tuned before being infiltrated by molten Li metal. The molten Li metal can be poured by capillary infusion of molten Li metal in liquid phase or infusion of molten Li metal droplets suspended in air. One or more of them enter the carbon support 702 to form Li metal vapor. Accurately tune the following conditions at the surface of the carbon stent 702 exposed to the incoming Li, including control: ● Atmospheric pollutants, such as moisture (H ₂ O vapor), oxygen (O), nitrogen (N) and combined Restrict or contain physiologically adsorbed or chemisorbed O hydrocarbons; ● Form nitrogen bonds on the surface during plasma post-treatment; and ● Purity of Li metal, such as controlling common surface oxides, nitrides and carbonates.

Li浸潤可藉由熔融Li金屬704、706之毛細管灌注來起始，以散佈於碳支架702內以及填充，從而形成鋰化碳化合物708，封裝碳支架702之空隙。程序之後可為非反應性Li潤濕浸潤及反應後處理。存在各種特定方法選擇，可經由該等選擇將Li浸潤於碳支架702中，該等選擇包括： ●            使用熔融Li金屬以在暴露碳表面處起始反應，假定將對照羥基(OH)及氧(O)吸附在碳支架702之暴露表面上的條件(諸如一或多種經組配以提供Li吸附中心的磷錳鋰礦官能化表面)，在約200℃下將碳支架702熱氧化還原或暴露於位於原始熔融Li金屬蒸氣之上持續例如30至45秒，可在碳支架702之暴露表面處起始化學反應以形成親核性表面，諸如LiC₆ ； ●            用表面活性元素塗佈暴露碳表面，以控制熔融Li金屬與暴露碳助熔元素之界面區域上之表面污染物可用於破壞氧化浮渣及/或促進包括氟(F)之鹵素的熔融，氧化物收氣劑可用於還原氧化(Ti，其他)； ●            藉由用諸如金屬之元素塗佈暴露碳表面來促進合金化及潤濕，該等元素具有比Li及/或促進Li潤濕及/或滲入之諸如矽(Si)鋁(Al)之元素低的表面能；以及 ●            將金屬粉末或諸如碳化矽(SiC)及其他物質之含金屬化合物併入碳預成型坯(諸如SiNP、Ni及其他)中以充當黏合劑且促進潤濕浸潤，從而允許取決於非反應性潤濕參數控制金屬與碳之比率。圖8A顯示根據一些實施方案之以碳為主之結構之浸潤速率之方程式，該以碳為主之結構具有由圖1A至圖1F中所示之3D以碳為主之粒子中的任一者或多者界定之空隙間距。Li infiltration can be initiated by capillary infusion of molten Li metals 704 and 706 to disperse and fill in the carbon stent 702 to form a lithiated carbon compound 708 to encapsulate the voids of the carbon stent 702. The procedure can be followed by non-reactive Li wetting and post-reaction treatment. There are various specific method options through which Li can be infiltrated into the carbon scaffold 702. These options include: ● Use molten Li metal to initiate the reaction at the exposed carbon surface, assuming that the hydroxyl (OH) and oxygen ( O) The conditions for adsorption on the exposed surface of the carbon support 702 (such as one or more phospho-manganese functionalized surfaces configured to provide Li adsorption centers), thermally redox or expose the carbon support 702 at about 200°C For example, 30 to 45 seconds above the original molten Li metal vapor, a chemical reaction can be initiated at the exposed surface of the carbon support 702 to form a nucleophilic surface, such as LiC ₆ ; ● The exposed carbon surface is coated with surface active elements , In order to control the surface contaminants on the interface area between molten Li metal and exposed carbon fluxing elements, it can be used to destroy the oxidized scum and/or promote the melting of halogens including fluorine (F). The oxide getter can be used to reduce oxidation ( Ti, others); ● Promote alloying and wetting by coating the exposed carbon surface with elements such as metals. These elements have better wetting and/or infiltration than Li and/or promote the wetting and/or penetration of aluminum such as silicon (Si) (Al) elements have low surface energy; and ● Incorporating metal powder or metal-containing compounds such as silicon carbide (SiC) and other substances into carbon preforms (such as SiNP, Ni, and others) to act as a binder and promote Wetting, thereby allowing the ratio of metal to carbon to be controlled depending on non-reactive wetting parameters. Figure 8A shows the equation of the infiltration rate of a carbon-based structure according to some embodiments, the carbon-based structure having any of the 3D carbon-based particles shown in Figures 1A to 1F Or more defined gap spacing.

圖8A顯示對將Li浸潤至當前呈現之以碳為主之結構之多孔區域中之任一者或多者中的速率進行建模的方程式，該等當前呈現之以碳為主之結構諸如為圖1A中所示之以碳為主之粒子100A之圖1F中所示之孔隙105F及相連路徑107。浸潤速率可受諸如熔融Li金屬之液態金屬之非反應性黏性阻力控制，隨後依照圖8A中所示之沃什伯恩方程式(Washburn's equation) 800A，液態金屬與碳接觸之間之化學反應得到碳化物，其中σ及η分別為液體之表面張力及黏度，θ為接觸角，且r_eff 為諸如圖1F中所示之孔隙105F之孔隙之有效孔隙半徑，該等孔隙可散佈在整個以碳為主之支架，諸如圖7中所示之以碳為主之支架702中。因此，如沃什伯恩方程式800A中所用之多種係數可見，毛細流動藉由將以碳為主之預形成物結構建模為理論平行圓柱管束進行描述，從而有效地表示滲入多孔材料中。Figure 8A shows an equation for modeling the rate of infiltration of Li into any one or more of the porous regions of the currently present carbon-based structure, such as The pore 105F and the connecting path 107 shown in FIG. 1F of the carbon-based particle 100A shown in FIG. 1A. The infiltration rate can be controlled by the non-reactive viscous resistance of the liquid metal such as molten Li metal, and then according to the Washburn's equation 800A shown in Figure 8A, the chemical reaction between the liquid metal and the carbon contact is obtained Carbides, where σ and η are the surface tension and viscosity of the liquid, θ is the contact angle, and r _eff is the effective pore radius of the pores such as the pore 105F shown in Figure 1F. The pores can be scattered throughout the entire carbon The main support, such as the carbon-based support 702 shown in FIG. 7. Therefore, as can be seen from the various coefficients used in Washburn equation 800A, capillary flow is described by modeling the carbon-based preform structure as a theoretical parallel cylindrical tube bundle, which effectively represents the penetration into the porous material.

圖8B顯示根據一些實施方案之包括非潤濕組配802B及自發潤濕組配804B之非反應性系統800B。舉例而言： ●            在非潤濕組配802B中，施加壓力(P₀ )以克服毛細管壓力，諸如由管之液體與固體壁之間之力之相互作用引起之薄管中二種不可混溶液體之間的壓力，且可受黏性摩擦限制，諸如已確定且由沃什伯恩方程式800A表徵之黏性摩擦；L可表示液相Li層，諸如由熔融Li金屬提供之液相Li層，S可表示暴露於L之固體碳表面，θ可表示L與S之接觸角，且V可表示黏性摩擦，且在L與S之接觸區域由沃什伯恩方程式800A表徵； ●            在自發潤濕組配804B中，θ維持在＜60°之角度，以達成以碳為主之支架之非反應性Li浸潤；且 ●            非潤濕組配802B或自發潤濕組配804B中之任一者或多者可併入或以其他方式實施於例示性以碳為主之支架806B中，其可為本發明所揭露之以碳為主之結構中之任一者或多者的形成部分。Figure 8B shows a non-reactive system 800B including a non-wetting composition 802B and a spontaneous wetting composition 804B according to some embodiments. For example: ● In the non-wetting assembly 802B, apply pressure (P ₀ ) to overcome capillary pressure, such as two immiscible solutions in a thin tube caused by the interaction of the force between the liquid and the solid wall of the tube The pressure between the bodies, and may be limited by viscous friction, such as the viscous friction that has been determined and characterized by Washburn equation 800A; L can represent a liquid Li layer, such as a liquid Li layer provided by molten Li metal , S can represent the solid carbon surface exposed to L, θ can represent the contact angle between L and S, and V can represent viscous friction, and the contact area between L and S is characterized by Washburn equation 800A; ● In spontaneous In the wetting set 804B, θ is maintained at an angle of <60° to achieve non-reactive Li infiltration of the carbon-based stent; and ● any of the non-wetting set 802B or the spontaneous wetting set 804B One or more may be incorporated or otherwise implemented in the exemplary carbon-based scaffold 806B, which may be a forming part of any one or more of the carbon-based structures disclosed in the present invention.

圖8C顯示根據一些實施方案之包括可潤濕反應性產物層組配802C及不可潤濕表面層組配804B之反應性系統800C。可潤濕反應性產物層組配802C可涉及形成新3D層806C，其類似於與圖6B2中所示之化學反應性系統600B2相關之先前所論述之層，其中新3D層604B2或化合物形成涉及基礎碳表面層604B2之至少部分消耗。本文中，固體碳材料S可被至少部分地消耗以製造或產生可為或包括LiC₆ 之新3D層806C。相比之下，在為S諸如在豎直方向直接面向之表面之不可潤濕表面層組配804B中，L不具反應性以使得L向毛細管管狀開放區域中之入侵引起與S之消耗反應來僅沿彼等毛細管開放區域產生新3D層808C。Figure 8C shows a reactive system 800C including a wettable reactive product layer assembly 802C and a non-wettable surface layer assembly 804B according to some embodiments. The wettable reactive product layer assembly 802C may involve the formation of a new 3D layer 806C, which is similar to the previously discussed layers related to the chemically reactive system 600B2 shown in FIG. 6B2, where the new 3D layer 604B2 or compound formation involves The base carbon surface layer 604B2 is at least partially consumed. Here, the solid carbon material S can be at least partially consumed to produce or produce a new 3D layer 806C _{that can be or include LiC 6.} In contrast, in the non-wettable surface layer assembly 804B for S such as the surface directly facing in the vertical direction, L is not reactive so that the invasion of L into the capillary tubular open area causes a depletion reaction with S. A new 3D layer 808C is created only along the open areas of their capillaries.

圖9顯示根據一些實施方案之鋰化及合金化以碳為主之結構之方法之流程圖900。在區塊902處，氧化物熱分解可用於藉由鋰(Li)蒸氣壓引發表面界面反應以活化經封裝預形成物中之碳表面。在區塊904處，在Li膜浸潤至金屬基體中之實例中，表面活性元素化合物可經氣化以分解氧化物助熔劑且/或促進潤濕。在區塊906處，作為浸潤過程之一部分，可併有諸如矽(Si)、鋁(Al)以及鉀(K)之合金元素以在界面處促進浸潤/管理氧氣活性。FIG. 9 shows a flowchart 900 of a method of lithiation and alloying a carbon-based structure according to some embodiments. At block 902, the thermal decomposition of the oxide can be used to initiate a surface interface reaction by lithium (Li) vapor pressure to activate the carbon surface of the packaged preform. At block 904, in the case where the Li film is infiltrated into the metal matrix, the surface active element compound may be vaporized to decompose the oxide flux and/or promote wetting. At block 906, as part of the infiltration process, alloying elements such as silicon (Si), aluminum (Al), and potassium (K) may be incorporated to promote infiltration/manage oxygen activity at the interface.

圖10A顯示根據一些實施方案之製備以碳為主之結構以經歷鋰化操作之方法1000A之流程圖。在區塊1002A處，可建立用於測試鋰箔/粉末預形成物之程序。在區塊1004A處，可使用替代金屬粉末預形成物以促進非反應性浸潤，同時理解諸如表面預處理/雜質管理之用於管理鋰之可再現方案。在區塊1006A處，可藉由經由包括熱重分析(TGA)及/或差示掃描量熱法(DSC)之各種技術量測熱活化反應來評估碳表面活性/預處理方案。FIG. 10A shows a flowchart of a method 1000A for preparing a carbon-based structure to undergo a lithiation operation according to some embodiments. At block 1002A, a procedure for testing lithium foil/powder preforms can be established. At block 1004A, alternative metal powder preforms can be used to promote non-reactive infiltration, while understanding reproducible solutions for lithium management such as surface pretreatment/impurity management. At block 1006A, the carbon surface activity/pretreatment scheme can be evaluated by measuring the thermal activation reaction through various techniques including thermogravimetric analysis (TGA) and/or differential scanning calorimetry (DSC).

圖10B顯示根據一些實施方案之製備適用於鋰化操作中之Li材料之另一方法1000B之流程圖。在區塊1002B處，可校準加熱壓板且可進行材料熱剖析。在區塊1004B處，可在測試之前、期間以及之後測定手套箱環境，諸如涉及濕度及氧氣之條件或設置。在區塊1006B處，可由鋰箔及/或金屬箔上之經氣化鋰、碳粉末以及其他物質中之任一者或多者製備樣品。10B shows a flowchart of another method 1000B for preparing Li materials suitable for lithiation operations according to some embodiments. At block 1002B, the heating platen can be calibrated and material thermal analysis can be performed. At block 1004B, the glove box environment, such as conditions or settings involving humidity and oxygen, can be measured before, during, and after the test. At block 1006B, samples can be prepared from any one or more of vaporized lithium, carbon powder, and other substances on the lithium foil and/or metal foil.

圖10C顯示以第一濃度位準成核多個碳粒子之方法1000C之流程圖。在區塊1002C處，可以經組配以在犧牲基體上形成第一膜之第一濃度位準成核多個碳粒子，碳粒子中之各者包含包括熔合在一起之多個少層石墨烯片之多個聚集體。在區塊1004C處，可基於熔合在一起之多個少層石墨烯片形成多孔結構。在區塊1006C處，可將熔融Li金屬灌注至多孔結構中。FIG. 10C shows a flowchart of a method 1000C for nucleating a plurality of carbon particles at a first concentration level. At block 1002C, a plurality of carbon particles can be nucleated at the first concentration level of the first film formed on the sacrificial substrate, and each of the carbon particles includes a plurality of small layers of graphene fused together Multiple aggregates of tablets. At block 1004C, a porous structure can be formed based on a plurality of few-layer graphene sheets fused together. At block 1006C, molten Li metal can be poured into the porous structure.

圖10D顯示以第二濃度位準成核多個碳粒子之方法1000D之流程圖。在區塊1002D處，可在第一膜上以第二濃度位準成核碳粒子。在區塊1004D處，可基於第二濃度位準之碳粒子形成第二膜。FIG. 10D shows a flowchart of a method 1000D for nucleating a plurality of carbon particles at a second concentration level. At block 1002D, carbon particles can be nucleated at a second concentration level on the first film. At block 1004D, a second film can be formed based on the carbon particles at the second concentration level.

圖10E顯示生長碳粒子之方法1000E之流程圖。在區塊1002處，可在卷軸式處理設備上生長碳粒子。Figure 10E shows a flowchart of a method 1000E for growing carbon particles. At block 1002, carbon particles can be grown on reel-type processing equipment.

圖10F顯示氣化熔融Li金屬之方法1000F之流程圖。在區塊1002E處，可將熔融Li金屬氣化至金屬箔上。在區塊1004E處，可將熔融Li金屬自金屬箔捲至多孔結構中。Figure 10F shows a flow chart of the method 1000F for vaporizing molten Li metal. At block 1002E, the molten Li metal can be vaporized onto the metal foil. At block 1004E, molten Li metal can be rolled from the metal foil into the porous structure.

圖10G顯示製備陽極以參與Li離子之可逆遷移之方法1000G之流程圖。在區塊1002G處，可製備陽極以與陰極一起參與Li離子之可逆遷移。藉由化學官能化或硫化中之任一者或多者製備陰極。Figure 10G shows a flow chart of a method 1000G for preparing an anode to participate in the reversible migration of Li ions. At block 1002G, an anode can be prepared to participate in the reversible migration of Li ions together with the cathode. The cathode is prepared by any one or more of chemical functionalization or vulcanization.

圖10H顯示使多個石墨烯薄片緻密之方法1000H之流程圖。在區塊1002H處，可在空隙結構上使多個石墨烯薄片緻密。FIG. 10H shows a flow chart of a method 1000H for densifying a plurality of graphene flakes. At block 1002H, a plurality of graphene flakes can be densified on the void structure.

圖10I顯示沈積第一多個碳粒子以形成第一膜之方法1000I之流程圖。在區塊1002I處，可沈積第一多個碳粒子以在基體上形成第一膜，第一膜經組配以提供第一導電性。在區塊1004I處，由可正交熔合在一起之少層石墨烯片形成之多個3D聚集體經組配以界定多孔結構。在區塊1006I處，多孔配置可形成於多孔結構中。在區塊1008I處，可將熔融Li金屬灌注至空隙結構中。FIG. 10I shows a flowchart of a method 1000I of depositing a first plurality of carbon particles to form a first film. At block 1002I, a first plurality of carbon particles may be deposited to form a first film on the substrate, and the first film is configured to provide a first conductivity. At block 1004I, multiple 3D aggregates formed from few graphene sheets that can be orthogonally fused together are assembled to define a porous structure. At block 10061, a porous configuration can be formed in the porous structure. At block 1008I, molten Li metal can be poured into the void structure.

圖10J顯示沈積第二多個碳粒子之方法1000J之流程圖。在區塊1002J處，可在第一膜上沈積第二多個碳粒子。在區塊1004J處，可基於第二多個碳粒子形成第二膜。Figure 10J shows a flow chart of a method 1000J for depositing a second plurality of carbon particles. At block 1002J, a second plurality of carbon particles may be deposited on the first film. At block 1004J, a second film may be formed based on the second plurality of carbon particles.

圖10K顯示浸潤熔融Li金屬之方法1000K之流程圖。在區塊1002K處，可將於氣相中之熔融Li金屬浸潤至空隙結構中。在區塊1004K處，可在由熔融Li金屬提供之任一個或多個Li離子與空隙結構之一或多個暴露表面之間引發化學反應。在區塊1006K處，可由一或多個暴露表面形成一或多個親鋰表面。Figure 10K shows a flow chart of a method 1000K for infiltrating molten Li metal. At block 1002K, the molten Li metal in the gas phase can be infiltrated into the void structure. At block 1004K, a chemical reaction can be initiated between any one or more Li ions provided by molten Li metal and one or more exposed surfaces of the void structure. At block 1006K, one or more lithium-philic surfaces can be formed from one or more exposed surfaces.

圖10L顯示塗佈親鋰表面中之任一個或多個之方法1000L之流程圖。在區塊1002L處，可用包括鹵素及包括鈦(Ti)之氧化物收氣劑中之任一者或多者之活性元素塗佈親鋰表面中之任一個或多個。Figure 10L shows a flowchart of a method 1000L for coating any one or more of the lithium-philic surfaces. At block 1002L, any one or more of the lithium-philic surfaces may be coated with active elements including any one or more of halogens and oxide getters including titanium (Ti).

圖10M顯示塗佈親鋰表面中之任一個或多個之方法1000M之流程圖。在區塊1002M處，可用包括矽(Si)或鋁(Al)之具有低於Li之表面能之任一個或多個元素塗佈親鋰表面中之任一個或多個。在區塊1004M處，可用具有低於Li之表面能之任一個或多個元素促進親鋰表面中之任一個或多個之Li潤濕增強。Figure 10M shows a flow chart of a method 1000M for coating any one or more of the lithium-philic surfaces. At block 1002M, any one or more of the lithium-philic surfaces can be coated with any one or more elements including silicon (Si) or aluminum (Al) having a surface energy lower than Li. At block 1004M, any one or more elements having a surface energy lower than Li can be used to promote the enhancement of Li wetting of any one or more of the lithium-philic surfaces.

圖10N顯示產生黏合劑之方法1000N之流程圖。在區塊1002N處，可藉由將金屬粉末或包括碳化矽(SiC)之含金屬化合物中之任一者或多者併入碳支架中來產生黏合劑。Figure 10N shows a flow chart of a method 1000N for producing adhesives. At block 1002N, the adhesive can be produced by incorporating any one or more of metal powder or a metal-containing compound including silicon carbide (SiC) into the carbon scaffold.

圖10O顯示添加一定量之摻雜劑之方法1000O之流程圖。在區塊1002O處，一定量之摻雜劑可處於界面處。在區塊1004O處，可影響對應於該量摻雜劑之Li潤濕之程度。FIG. 10O shows a flow chart of the method 1000O of adding a certain amount of dopant. At block 1002O, a certain amount of dopant may be at the interface. At block 1004O, the degree of Li wetting corresponding to the amount of dopant can be affected.

圖10P顯示控制羥基(hydroxy/hydroxyl，OH)吸附之方法1000P之流程圖。在區塊1002P處，可在空隙結構之一或多個暴露表面中之任一個處控制羥基(OH)吸附。Figure 10P shows a flow chart of 1000P for controlling the adsorption of hydroxy/hydroxyl (OH). At block 1002P, hydroxyl (OH) adsorption can be controlled at any one of one or more exposed surfaces of the void structure.

圖11A顯示灌注鋰之方法1100A之流程圖。在區塊1102A處，可藉由使用卷軸式鍋爐硬焊或自發性浸潤來灌注鋰。在區塊1104A處，可使用具有2D液體間隙填充劑之二維(2D)類似物。在區塊1106A處，可在液體與固體界面處使所灌注之鋰金屬與暴露碳表面進行化學反應，且控制用於活化之助熔劑、增大及/或減小表面張力且控制熱力學動力。在區塊1108A處，可在熱板上有Li箔/碳粒子堆疊之情況下藉由使用鹵素中間層以分解Li₂ O來進行鋰可濕性之快速篩檢。FIG. 11A shows a flow chart of a method 1100A for infusing lithium. At block 1102A, lithium can be poured by brazing or spontaneous infiltration using a reel boiler. At block 1104A, a two-dimensional (2D) analog with a 2D liquid gap filler can be used. At block 1106A, the injected lithium metal can be chemically reacted with the exposed carbon surface at the liquid-solid interface, and the flux used for activation can be controlled, the surface tension can be increased and/or reduced, and the thermodynamic power can be controlled. At block 1108A, a rapid screening of lithium wettability can be performed _{by using a halogen intermediate layer to decompose Li 2} O when there is a Li foil/carbon particle stack on the hot plate.

圖11B顯示將鋰(Li)氣化至金屬箔上之方法1100B之流程圖。在區塊1102B處，可將鋰氣化至金屬箔上，該金屬箔可充當熱導體。在區塊1104B處，可任擇地使用銅作為集電器且/或使用鉭以用於釋放來達成極少化學相互作用。在區塊1106B處，可調諧與經封裝以碳為主之粒子及/或結構中之孔隙體積相稱之膜厚度。FIG. 11B shows a flowchart of a method 1100B for vaporizing lithium (Li) onto a metal foil. At block 1102B, lithium can be vaporized onto the metal foil, which can act as a thermal conductor. At block 1104B, copper may optionally be used as a current collector and/or tantalum may be used for release to achieve minimal chemical interaction. At block 1106B, the film thickness commensurate with the pore volume in the encapsulated carbon-based particles and/or structure can be tuned.

圖11C顯示製備碳粒子以諸如經由稱為預鋰化之方法進行鋰化之方法1100C之又另一流程圖。在區塊1102C處，可在乾室環境條件中用要被施用之負載物(諸如砑光卷軸型)定向處於碳粒子填充床頂部上或經預鋰化及/或預成型之箔。在區塊1104C處，可在集中負載位置處有快速熱尖峰之情況下跨Li及經封裝粒子產生總體類等溫條件(諸如在約180℃下及/或緊接著低於Li熔點)。在區塊1106C處，可利用與伴以可變滲透性之達西定律(Darcy's law)、Washburn等相關之原理使用放熱反應以引發浸潤、接著為於多孔碳介質中之毛細管驅動流體流動。毛細管驅動流體流動假設無可觀反應產物形成/堆積。FIG. 11C shows yet another flow chart of a method 1100C for preparing carbon particles for lithiation such as through a method called prelithiation. At block 1102C, a load to be applied (such as a calender reel type) can be oriented on top of a packed bed of carbon particles or a pre-lithiated and/or pre-formed foil in dry room environmental conditions. At block 1104C, general isothermal conditions (such as at about 180°C and/or immediately below the melting point of Li) can be generated across Li and the encapsulated particles with rapid thermal spikes at the concentrated load location. At block 1106C, the principles related to Darcy's law, Washburn, etc. with variable permeability can be used to use exothermic reactions to initiate infiltration, followed by capillary in the porous carbon medium to drive fluid flow. Capillary-driven fluid flow assumes that no appreciable reaction products are formed/accumulated.

圖12顯示根據一些實施方案之在用氣化Li形成碳粒子期間執行碳粒子之Li灌注之方法1200之流程圖。在區塊1202處，可諸如在真空氣化器中用鋰塗佈金屬(諸如銅及/或鉭)箔；諸如厚度及密度之所量測Li體積可與經封裝粒子層中之孔隙體積相稱。在區塊1204處，可在無黏合劑之情況下諸如經由尺寸放大、由細粒產生粗粒狀材料(諸如膜)來將粒子裝配至經封裝膜中，其中裝配技術可包括翻滾、壓力壓緊、熱反應、熔合、乾燥、由液體懸浮液進行之黏聚以及用以形成硬幣孔尺寸圓片之靜電。在區塊1206處，可形成固有碳粒子。在區塊1208處，可使形成期間之碳之sp² /sp³ 比最佳化以相對應地增加鋰(Li)***及/或間夾。在區塊1210處，可減少雜質污染，諸如由乙炔及其他電漿後芳族物造成之雜質污染。在區塊1212處，可執行後處理操作。FIG. 12 shows a flowchart of a method 1200 for performing Li pouring of carbon particles during the formation of carbon particles with vaporized Li according to some embodiments. At block 1202, a metal (such as copper and/or tantalum) foil can be coated with lithium, such as in a vacuum carburetor; the measured Li volume such as thickness and density can be commensurate with the pore volume in the encapsulated particle layer . At block 1204, the particles can be assembled into the encapsulated film, such as through size enlargement, and coarse-grained materials (such as films) produced from fine particles without adhesives. The assembly techniques can include tumbling, pressure pressing Tightening, thermal reaction, fusion, drying, cohesion from a liquid suspension, and static electricity used to form coin-hole size discs. At block 1206, inherent carbon particles can be formed. At block 1208, the sp ² /sp ³ ratio of carbon during formation can be optimized to increase lithium (Li) insertion and/or intercalation correspondingly. At block 1210, impurity pollution, such as impurity pollution caused by acetylene and other post-plasma aromatics, can be reduced. At block 1212, post-processing operations can be performed.

圖13顯示示出根據一些實施方案之具有其中併有3D以石墨烯為主之奈米結構1302以為陽極1300提供結構界定之理想化陽極1300組配的示意圖。可將3D以石墨烯為主之奈米結構1302併入本發明所揭露之以碳為主之結構中之任一個或多個中或為其提供結構界定，該等本發明所揭露之以碳為主之結構包括均示於圖1F中之孔隙105F及/或相連路徑107F，且可限制或以其他方式保留諸如矽(Si)之金屬摻雜劑1312且產生經表面活化擴散路徑1316以處置Li離子1306合金化-去合金化循環期間之體積擴增且亦限制電解質進入。如路徑1310中所示，矽可被再分佈至少層石墨烯片中之缺陷、孔隙或褶皺中且在路徑1308中分佈至諸如高度極性聚丙烯腈(PAN)之黏合劑1304中。硫(S)摻雜可被執行或發生在石墨烯1314與矽接觸區或表面處以輔助Li S電池系統中之Li複合及相關充電-放電循環來達成本文所引用之效能圖中之任一個或多個，包括大於372 mAh/g之比容量，該比容量一般可藉由單獨石墨作為理論最大值達成。在一些實施方案中，除少層石墨烯之外或作為少層石墨烯之替代物，可使用氧化石墨烯，且可將Li S系統浸入LiPF₆ 液相電解質中。FIG. 13 shows a schematic diagram illustrating an idealized anode 1300 assembly with a 3D graphene-based nanostructure 1302 incorporated therein to provide a structural definition of the anode 1300 according to some embodiments. The 3D graphene-based nanostructure 1302 can be incorporated into any one or more of the carbon-based structures disclosed in the present invention or provided with a structure definition. The carbon-based structures disclosed in the present invention The main structure includes the pore 105F and/or the connecting path 107F shown in FIG. 1F, and can limit or otherwise retain the metal dopant 1312 such as silicon (Si) and create a surface activated diffusion path 1316 for disposal Li ions 1306 increase in volume during the alloying-dealloying cycle and also restrict electrolyte entry. As shown in path 1310, silicon can be redistributed in defects, pores, or wrinkles in at least one layer of graphene sheet and distributed in path 1308 into a binder 1304 such as highly polar polyacrylonitrile (PAN). Sulfur (S) doping can be performed or occurs at the contact area or surface of the graphene 1314 and silicon to assist Li recombination and related charge-discharge cycles in the Li S battery system to achieve any of the performance graphs cited herein or Many, including a specific capacity greater than 372 mAh/g, which can generally be achieved by using graphite alone as the theoretical maximum. In some embodiments, in addition to or as an alternative to the few-layer graphene, graphene oxide may be used, and the LiS system may be immersed in the LiPF ₆ liquid electrolyte.

陽極1300可經組配有現有或即將研發之未來以碳為主之材料，此舉提供反向相容性。經表面活化擴散路徑1316可容納Li金屬，而Li亦可間夾於少層石墨烯片對之間。碳材料之孔隙尺寸可在陽極1300中經調諧以達成Li之特定分佈或圍阻位準以及Li離子流動可逆性，且可以非晶碳或結晶碳結構創造。The anode 1300 can be assembled with existing or to-be-developed future carbon-based materials, which provides reverse compatibility. The surface activated diffusion path 1316 can contain Li metal, and Li can also be sandwiched between pairs of few graphene sheets. The pore size of the carbon material can be tuned in the anode 1300 to achieve a specific distribution or containment level of Li and the reversibility of Li ion flow, and can be created with amorphous carbon or crystalline carbon structures.

陽極1300之預鋰化最初可包括熔融Li金屬電化或與熔融Li金屬之直接接觸以稍後過渡至直接蒸氣灌注技術。如先前實質上所描述，用作用於構建陽極1300之形成材料之碳結構可直接沈積為粒子膜或由粉末沈積為粒子膜。Li滲出速率可匹配陽極1300內之Li***速率以避免過量暴露於進入Li之Li沈積或縮合碳表面。且陽極1300之生產及成本度量考慮因素可包括： ●            以低成本粉末而非膜形式產生以碳為主之材料，該等低成本粉末經組配以被滴加至現有Li離子或Li S電池製造中； ●            不依賴於黏合劑在轉鼓上直接沈積以碳為主之膜；以及 ●            將Li灌注至諸如漿料澆鑄膜/黏合劑之以碳為主之粒子及結構中，可使用蒸發技術以純化或乾燥碳。The pre-lithiation of the anode 1300 may initially include electrolysis of molten Li metal or direct contact with molten Li metal to later transition to a direct vapor infusion technique. As substantially described previously, the carbon structure used as a forming material for constructing the anode 1300 can be directly deposited as a particle film or deposited as a particle film from a powder. The Li exudation rate can match the Li insertion rate in the anode 1300 to avoid excessive exposure to the Li deposited or condensed carbon surface entering Li. And the production and cost measurement considerations of anode 1300 may include: ● Carbon-based materials are produced in the form of low-cost powders instead of membranes, and these low-cost powders are assembled to be dripped into existing Li-ion or Li S battery manufacturing; ● Do not rely on the direct deposition of a carbon-based film on the drum by the adhesive; and ● Infusion of Li into carbon-based particles and structures such as slurry casting film/adhesives, evaporation technology can be used to purify or dry the carbon.

陽極1300之Li灌注可包括藉由已知卷軸式鍋爐硬焊及/或自發性浸潤技術建立之以下程序，該等以下程序包括以下中之任一者或多者： ●            使用具有2D液體間隙填充劑之二維(2D)類似物； ●            使用用於活化之助熔劑進行之液體與固體化學反應； ●            增加一定比例之固體至黏性表面積且減少一定比例之液體至黏性表面積以控制且調諧表面張力及/或熱力學動力；以及 ●            在熱板上有Li箔/碳粒子堆疊之情況下使用鹵素中間層以分解任何所形成之氧化鋰(Li₂ O)來篩檢Li可濕性。Li pouring of anode 1300 may include the following procedures established by known reel-type boiler brazing and/or spontaneous infiltration techniques. The following procedures include any one or more of the following: ● Use of 2D liquid gap filling Two-dimensional (2D) analogues of agents; ● Chemical reaction between liquid and solid using flux for activation; ● Increase a certain proportion of solid to viscous surface area and reduce a certain proportion of liquid to viscous surface area to control and tune Surface tension and/or thermodynamic power; and ● Use a halogen intermediate layer to decompose any formed lithium oxide (Li ₂ O) when there is a Li foil/carbon particle stack on the hot plate to screen the Li wettability.

陽極1300之Li灌注亦可包括與Li向經組配以充當熱導體之金屬箔上之氣化相關之以下程序、技術或實施方案： ●            選擇銅(Cu)以在併有陽極1300之Li離子或Li S電池系統中用作集電器； ●            鉭(Ta)散佈於陽極1300內以用於Li離子釋放，產生最少總體化學相互作用；以及 ●            產生與經封裝粒子中之孔隙體積相稱之以碳為主之膜厚度。The Li pouring of the anode 1300 may also include the following procedures, techniques, or implementations related to the vaporization of Li onto the metal foil that is assembled to serve as a thermal conductor: ● Choose copper (Cu) to be used as a current collector in a Li ion or Li S battery system with anode 1300; ● Tantalum (Ta) is dispersed in the anode 1300 for the release of Li ions, resulting in the least overall chemical interaction; and ● Produce a carbon-based film thickness commensurate with the pore volume in the encapsulated particles.

此外，陽極1300之Li灌注亦可包括與Li及Ta箔於以床組配形式封裝之碳粒子頂部上之定向相關之以下程序、技術或實施方案，該床組配可在乾室環境條件中被製備成接納由旋轉砑光卷軸型轉鼓提供之負荷或壓力： ●            包覆有一層Ta箔、進一步包覆於Li箔中之砑光卷軸或轉鼓之正向旋轉壓縮以薄層材料形式製備之碳粒子，該薄層材料被置放於銅箔上，其中由砑光卷軸施加熱且向Cu箔施加熱以熔融Li且產生浸潤至碳粒子中之熔融Li金屬； ●            跨經浸潤Li及經封裝碳粒子產生諸如在約180℃下、僅低於Li熔點之總體等溫條件； ●            在集中Li負載位置處觀測到快速熱尖峰；以及 ●            如藉由伴以可變滲透性之達西定律、沃什伯恩方程式等中之任一者或多者所控管之用放熱反應進行之Li浸潤及於多孔碳介質中之毛細管驅動熔融Li金屬流體流動，方法假設無可觀反應產物形成或堆積。In addition, the Li pouring of the anode 1300 can also include the following procedures, techniques or implementations related to the orientation of Li and Ta foil on top of the carbon particles encapsulated in the form of a bed assembly, which can be in a dry room environment. Prepared to accept the load or pressure provided by the rotating calender reel drum: ● The carbon particles prepared in the form of a thin layer of material are compressed by the positive rotation of a calender reel or drum covered with a layer of Ta foil and further wrapped in the Li foil, and the thin layer of material is placed on the copper foil. Applying heat from the calender reel and applying heat to the Cu foil to melt Li and produce molten Li metal that is infiltrated into the carbon particles; ● Across the infiltrated Li and the encapsulated carbon particles, an overall isothermal condition such as at about 180°C and only below the melting point of Li is generated; ● A rapid thermal spike is observed at the location of the concentrated Li load; and ● For example, Li infiltration by exothermic reaction and capillary-driven melting in porous carbon medium controlled by any one or more of Darcy's law and Washburn's equation with variable permeability The Li metal fluid flows, and the method assumes that no appreciable reaction products form or accumulate.

再此外，陽極1300之Li灌注亦可包括以下程序、技術或實施方案： ●            在真空氣化器中用鋰Li塗佈金屬(諸如銅(Cu)及/或鉭(Ta))箔；控制與經封裝碳粒子層或膜中之孔隙體積相稱之諸如厚度及密度之Li體積； ●            在無黏合劑之情況下將碳粒子裝配至經封裝膜中，但假設與熔融Li不存在相互作用且所提出之黏合劑可在Li浸潤之後易於移除，可考慮黏合劑選項； ●            由碳細粒放大及/或產生粗粒狀碳材料(諸如膜)，此係諸如藉由翻滾、壓力壓緊、熱反應、熔合、乾燥、由液體懸浮液進行之黏聚以及用以生成塑形為圓片之硬幣孔尺寸結構之靜電來進行； ●            在反應器內收集或篩檢前述材料中之任一種； ●            執行後微波燒結或熔合；以及 ●            不依賴於碳模具執行成圓片或錠狀物之部分壓緊。In addition, Li pouring of anode 1300 can also include the following procedures, techniques or implementations: ● Coating metal (such as copper (Cu) and/or tantalum (Ta)) foil with lithium Li in a vacuum carburetor; controlling the thickness and density of Li commensurate with the pore volume in the encapsulated carbon particle layer or film volume; ● Assemble carbon particles into the encapsulated film without adhesive, but assuming that there is no interaction with molten Li and the proposed adhesive can be easily removed after Li infiltration, adhesive options can be considered; ● Amplification and/or production of coarse-grained carbon materials (such as films) from fine carbon particles, such as by tumbling, pressure compaction, thermal reaction, fusion, drying, cohesion by liquid suspension, and production The shape of the coin hole size structure of the disc is carried out by static electricity; ● Collect or screen any of the aforementioned materials in the reactor; ● Microwave sintering or fusion after implementation; and ● It does not rely on the partial compaction of the carbon mold into a wafer or ingot.

用於形成陽極1300之少層石墨烯及其他碳之固有碳粒子形成可包括： ●            最佳化sp² 及/或sp³ 碳結構形成以增加鋰***/間夾；以及 ●            減少諸如乙炔及其他電漿後芳族物之雜質污染。The formation of intrinsic carbon particles of the few layers of graphene and other carbon used to form the anode 1300 can include: ● optimizing the formation of sp ² and/or sp ³ carbon structures to increase lithium insertion/intercalation; and ● reducing such as acetylene and others Impurity contamination of aromatics after plasma.

後處理方法可包括： ●            洗滌芳族物，諸如移除芳族物； ●            在約500℃下烘烤碳約3小時持續時間以移除所吸附之濕度及/或氧氣；以及 ●            用一氧化矽氮化及/或處理碳。Post-processing methods can include: ● Washing aromatics, such as removing aromatics; ● Bake the carbon at about 500°C for about 3 hours to remove the adsorbed humidity and/or oxygen; and ● Nitriding and/or treating carbon with silicon monoxide.

影響Li浸潤至陽極1300之碳結構中之因素可包括： ●            前驅體體積； ●            熔融溫度，諸如約180℃至380℃； ●            粒子後處理，諸如在經暴露以與Li接觸之碳表面處進行； ●            機械壓力； ●            石墨烯特性，諸如少層或片尺寸； ●            碳結構形態，包括孔隙尺寸、體積、分佈；以及 ●            表面活化。Factors affecting Li infiltration into the carbon structure of anode 1300 can include: ● Precursor volume; ● Melting temperature, such as about 180°C to 380°C; ● Particle post-processing, such as on the surface of the carbon exposed to come into contact with Li; ● Mechanical pressure; ● Graphene characteristics, such as few layers or sheet size; ● Carbon structure morphology, including pore size, volume, and distribution; and ● Surface activation.

對Li浸潤之碳結構反應可包括： ●            自發性浸潤； ●            積聚過量Li材料以達成與Li輸入成比例之平衡質量；以及 ●            基於對照碳結構總體積比較之暴露於進入Li之碳表面積之比之浸潤程度。The carbon structure reaction to Li infiltration can include: ● Spontaneous infiltration; ● Accumulate excessive Li materials to achieve a balanced quality proportional to Li input; and ● The degree of infiltration of the ratio of the carbon surface area exposed to Li based on the comparison of the total volume of the control carbon structure.

圖14顯示根據一些實施方案之在充電-放電循環數內比較以mAh/g為單位之陽極比容量之矽及碳(Si-C)陽極效能。包括426、459、462、486、487以及401之所示各種系列可包括與示於圖13中之陽極1300或併於Li離子或Li S系統陽極內之示於圖1A至圖1F中之碳結構中之任一個或多個類似的變化及/或製備。如所示，本發明所揭露之碳結構可均一地產生顯著地高於如通常與石墨陽極相關聯之372 mAh/g之比容量值。Figure 14 shows a comparison of silicon and carbon (Si-C) anode performance in mAh/g over the number of charge-discharge cycles according to some embodiments. The various series including 426, 459, 462, 486, 487, and 401 may include the anode 1300 shown in FIG. 13 or the carbon shown in FIGS. 1A to 1F combined in the Li ion or Li S system anode. Any one or more similar changes and/or preparations in the structure. As shown, the carbon structure disclosed in the present invention can uniformly generate a specific capacity value that is significantly higher than 372 mAh/g, which is commonly associated with graphite anodes.

圖15及16顯示根據一些實施方案之與示於圖15中之理想化陰極組配1500相關之示意圖，其特點在於於藉由PAN型黏合劑固持在一起且浸沒於LiTFSI電解質溶液中以提供便利Li離子運輸及電傳導之石墨烯片中之分散硫化鋰(Li₂ S)奈米粒子以及在Li S電池系統充電-放電循環中生成之聚硫化物(PS)減少及控制。在Li S電池系統中，理想化陰極組配1500可至少部分用本發明所揭露之碳結構中之任一個或多個來實施，該等本發明所揭露之碳結構中之任一個或多個包括在內以形成圖1F中所示之孔隙105F及/或相連微結構107F。圖16顯示例示性原位3D奈米結構化少層石墨烯材料1600，其可併有在內以向本發明所揭露之碳結構中之任一個或多個提供結構界定。在一些實施方案中，少層石墨烯片堆疊1602可包括於二階段高溫(HT)法至250℃及350℃下被加熱之經碾磨之硫浸漬石墨烯。少層石墨烯片堆疊1602可被Li浸潤，該Li諸如為由含三乙基硼氫化鋰(LiEt₃ BH)之THF溶液或設置在惰性氬氣(Ar)氛圍中以藉由前述Li浸潤技術中之任一種或多種提供Li源1604之正丁基鋰提供之Li。少層石墨烯片之經Li浸潤堆疊1602可經歷在110℃下10小時之HT真空處理以在孔隙，諸如示於圖1F中之孔隙105F中原位形成Li₂ S，其中該Li₂ S參與如先前所描述之Li S電化電池運作。15 and 16 show schematic diagrams related to the idealized cathode assembly 1500 shown in FIG. 15 according to some embodiments, which are characterized in that they are held together by a PAN-type adhesive and immersed in a LiTFSI electrolyte solution for convenience _{The reduction and control of the dispersed lithium sulfide (Li 2} S) nanoparticles in the graphene sheet for Li ion transport and electrical conduction and the polysulfide (PS) generated during the charge-discharge cycle of the Li S battery system. In the Li S battery system, the idealized cathode assembly 1500 can be implemented at least in part by any one or more of the carbon structures disclosed in the present invention, and any one or more of the carbon structures disclosed in the present invention It is included to form the pore 105F and/or the connected microstructure 107F shown in FIG. 1F. FIG. 16 shows an exemplary in-situ 3D nanostructured few-layer graphene material 1600, which can be incorporated to provide structure definition to any one or more of the carbon structures disclosed in the present invention. In some embodiments, the few-layer graphene sheet stack 1602 may include milled sulfur-impregnated graphene heated in a two-stage high temperature (HT) process to 250°C and 350°C. The few-layer graphene sheet stack 1602 can be infiltrated by Li, such as a _{THF solution containing lithium triethylborohydride (LiEt 3} BH) or placed in an inert argon (Ar) atmosphere to be infiltrated by the aforementioned Li infiltration technique Any one or more of the Li source 1604 provides Li provided by n-butyllithium. The Li-infiltrated stack 1602 of the few-layer graphene sheets can undergo HT vacuum treatment at 110°C for 10 hours to form Li ₂ S in situ in the pores, such as the pore 105F shown in FIG. 1F, where the Li ₂ S participates in The Li S electrochemical battery described previously operates.

圖17A顯示以碳為主之粒子100A、100E及/或其類似物之經放大透視剖視圖。如結合示於圖1A至圖1F中之以碳為主之粒子100A所論述由石墨烯片之導電互連黏聚體101B之間之接觸表面及/或區域形成之個別紐帶1702A可延伸以形成部分1700A之晶格及/或樹狀分支結構，Li離子(Li+) 1704A可通過該晶格及/或樹狀分支結構間夾、***於包含石墨烯片之3D束101B之部分1700A之個別梯度層之間。電流可經由電子流動通過石墨烯片之互連3D束101B之間之接觸表面及/或區域來進行。Li離子可流過尺寸設定為如圖1A至1F中所描述之空隙或孔隙雙峰分佈之約20奈米至50奈米較大尺寸的孔隙1710A，或諸如經由化學微米限制而被限制在尺寸一般約1奈米至3奈米之孔隙中。FIG. 17A shows an enlarged perspective cross-sectional view of carbon-based particles 100A, 100E, and/or the like. As discussed in conjunction with the carbon-based particles 100A shown in FIGS. 1A to 1F, the individual bonds 1702A formed by the contact surfaces and/or regions between the conductive interconnection aggregates 101B of the graphene sheet can be extended to form Part of the 1700A crystal lattice and/or tree-like branch structure. Li ions (Li+) 1704A can be inserted between the crystal lattice and/or tree-like branch structure and inserted into the individual gradients of the part 1700A of the 3D beam 101B containing graphene sheets Between layers. Electric current can be conducted through the flow of electrons through the contact surfaces and/or areas between the interconnected 3D beams 101B of the graphene sheets. Li ions can flow through pores 1710A with a larger size of about 20 nm to 50 nm, which are set to have a bimodal distribution of pores or pores as described in Figures 1A to 1F, or are restricted in size such as through chemical micron confinement. Generally about 1 nanometer to 3 nanometers in the pores.

因此，Li離子流動可在以碳為主之粒子100A中視需要精細受控或經調諧以例如與電子流動在直徑上相反來促進可為通過石墨烯片之3D束101B之接觸點及/或區域之電傳導及/或電子流動必需的電化梯度。個別以碳為主之紐帶之間之間距可設置為0.1 µm。熟習此項技術者應瞭解，僅舉例而言，提供0.1 µm之尺寸，且其他合適之類似或相異尺寸可存在於以碳為主之粒子100A之部分1700A中。Therefore, the flow of Li ions can be finely controlled or tuned as needed in the carbon-based particles 100A, for example, to be diametrically opposed to the flow of electrons to facilitate the contact points and/or areas that can be the 3D beam 101B through the graphene sheet The electrochemical gradient necessary for electrical conduction and/or electron flow. The distance between individual carbon-based bonds can be set to 0.1 µm. Those familiar with this technology should understand that, for example, a size of 0.1 µm is provided, and other suitable similar or different sizes may exist in the part 1700A of the carbon-based particle 100A.

部分1700A可由彼此燒結在一起以形成以下組配之石墨烯片之3D束101B形成：其中不存在完全開放通道以使得必須傳導電通過石墨烯片之互連3D束101B之接觸點及/或區域。因此，穿過空隙1704A之液體及碳-碳鍵結之傳導性質促進在化學黏合劑及/或化學黏合材料或試劑不必要之情況下以碳為主之材料與其他以碳為主之材料之連接，許多該化學黏合劑及/或化學黏合材料或試劑產生以碳為主之粒子100A之非所需化學性質或關於其功能之副作用。The part 1700A can be formed by sintering each other to form the 3D beam 101B of graphene sheets in the following configuration: where there are no completely open channels so that electricity must be conducted through the contact points and/or areas of the interconnected 3D beam 101B of the graphene sheets . Therefore, the conductive properties of the liquid and the carbon-carbon bond passing through the gap 1704A promote the difference between carbon-based materials and other carbon-based materials when chemical bonding agents and/or chemical bonding materials or reagents are not necessary. In connection, many of the chemical adhesives and/or chemical adhesive materials or reagents produce undesirable chemical properties of the carbon-based particles 100A or side effects related to their functions.

以碳為主之粒子100A之開放多孔支架102A呈現與傳統工業標準電池電極之偏離，該等傳統工業標準電池電極可涉及被雜亂地組織在基體上之漿料澆鑄巨礫、相對大粒子，該等巨礫通常需要黏合劑固持在一起以傳導電通過其。由以碳為主之粒子100A之階層式孔隙101A及/或相連微結構107F界定之開放多孔支架102A允許於其中之電傳導改進。The open porous scaffold 102A of carbon-based particles 100A exhibits a deviation from the traditional industry standard battery electrodes, which may involve slurry-cast boulders and relatively large particles that are disorderly organized on the substrate. Boulders usually require an adhesive to hold them together in order to conduct electricity through them. The open porous scaffold 102A defined by the hierarchical pores 101A of the carbon-based particles 100A and/or the connected microstructures 107F allows the electrical conduction therein to be improved.

圖17B顯示伴以石墨烯上加石墨烯緻密化之圖17A之以碳為主之粒子。對於圖17B之實例，邊緣區域處之示於圖17B中之表面1700B及/或示於圖17A中之表面1708A可在多個額外石墨烯層之應用、沈積或以其他方式生長時緻密化，該等邊緣區域為以碳為主之粒子100A之部分1700A之分支樹狀結構之至少部分地平坦表面。該等緻密方法(process/method)及/或程序准許產生包含石墨烯片之3D束101B之組合之錯綜複雜、多層且潛在地幾乎無限可調諧3D碳結構。因此，當將以碳為主之粒子100整合至電池電極中時，藉由石墨烯上加石墨烯緻密化實現之該精細可調諧性可促進達到特別導電性值。Figure 17B shows the carbon-based particles of Figure 17A accompanied by graphene densification by adding graphene. For the example of FIG. 17B, the surface 1700B shown in FIG. 17B and/or the surface 1708A shown in FIG. 17A at the edge region can be densified during the application, deposition, or growth of multiple additional graphene layers, The edge regions are at least partly flat surfaces of the branched tree-like structure of the portion 1700A of the carbon-based particle 100A. These processes/methods and/or procedures permit the creation of intricate, multi-layered, and potentially almost infinitely tunable 3D carbon structures of combinations of 3D bundles 101B containing graphene sheets. Therefore, when the carbon-based particles 100 are integrated into the battery electrode, the fine tunability achieved by adding graphene to the graphene densification can promote the achievement of a special conductivity value.

圖18A至圖18C分別顯示本發明所揭露之碳結構中之任一個或多個，包括分別示於圖1A及1F中之以碳為主之粒子100A及/或相連微結構107F之在各種漸增放大位準下之真實顯微圖1800A、1800B以及1800C。18A to 18C respectively show any one or more of the carbon structures disclosed in the present invention, including the carbon-based particles 100A and/or the connected microstructures 107F shown in FIGS. 1A and 1F, respectively. Real micrographs 1800A, 1800B, and 1800C at the increased magnification level.

圖18D顯示顯微圖1800D，其中複合碳黏聚體具有與針對以碳為主之粒子100A所描述之內部結構類似之內部結構，完整地具有孔隙105F及相連微結構107F，且尺寸及組成均已被製備以併入Li離子系統之陰極中，但亦可適用於方法且產生用於陽極上之Li之籠。可使用尺寸經無規設定且經塑形之黏聚體以製造本發明所揭露之電極中之任一種或多種。儘管如此，調諧程序可允許產生亦呈規則預期尺寸之碳黏聚體及/或粒子，潛在地提供處置容易性及處理優勢。Figure 18D shows a micrograph 1800D, in which the composite carbon cohesive has an internal structure similar to the internal structure described for the carbon-based particle 100A, complete with pores 105F and connected microstructures 107F, and the size and composition are all It has been prepared for incorporation into the cathode of the Li ion system, but can also be adapted to the method and produce a cage of Li for use on the anode. Any one or more of the electrodes disclosed in the present invention can be manufactured by using randomly set and shaped adhesives. Nonetheless, the tuning procedure may allow the generation of carbon cohesives and/or particles that are also regular expected sizes, potentially providing ease of handling and processing advantages.

圖18E顯示顯微圖1800E，其中如藉由本發明所揭露之以碳為主之結構中之至少任一個或多個，包括示於圖1F中之相連微結構107F所描述，活性碳結構用以浸潤用於Li S系統陰極中之硫(S)。顯微圖1800E中所示之用以浸潤硫(S)之活性碳結構可藉由合併螺旋式傳送機系統或經由其他不同步驟產生。熱反應器產生之材料已顯示為比未經摻雜及/或未經官能化之微波生成之碳結構更加親鋰。在一些實施方案中，在反應器中產生之少層石墨烯表面上之以有機物及/或烴為主之污染盛行可能需要執行額外後處理改進步驟。Figure 18E shows a micrograph 1800E, in which as described by at least any one or more of the carbon-based structures disclosed by the present invention, including the connected microstructure 107F shown in Figure 1F, the activated carbon structure is used Wetting the sulfur (S) used in the cathode of the Li S system. The activated carbon structure for infiltration of sulfur (S) shown in the micrograph 1800E can be produced by incorporating a screw conveyor system or through other different steps. The material produced by the thermal reactor has been shown to be more lithium-philic than the microwave-generated carbon structure without doping and/or functionalization. In some embodiments, the prevalence of organic and/or hydrocarbon-based contamination on the surface of the few-layer graphene produced in the reactor may require additional post-processing improvement steps.

圖19A顯示諸如碳支架300B之3D石墨烯-粒子陰極支架之示意性描繪1900A，該碳支架300B之特徵在於適用於按比例放大之於其中之硫(S)微米限制及/或本發明所揭露之碳中之任一個或多個併有，包括用作用以產生示於圖1F中之相連微結構107F之形成材料。在圖19A之實例中，顯示具有各種厚度1904A及1906A之呈各種3D陰極支架型結構或組配之含有硫夾帶及/或限制1902A之以石墨烯為主之片材及/或結構。S包括於以石墨烯為主之電池化學物質中提供所需電荷儲存及駐存，該所需電荷儲存及駐存係以毫安小時為單位來量測，進一步由藉由用經碳黑奈米粒子裝飾之輕度氧化氧化石墨烯片包覆聚(乙二醇) (PEG)塗佈的亞微米硫粒子進行的石墨烯-硫複合材料合成加以描述。Figure 19A shows a schematic depiction 1900A of a 3D graphene-particle cathode stent such as a carbon stent 300B. The carbon stent 300B is characterized by the sulfur (S) micron limit in which it is suitable for scale up and/or disclosed in the present invention The combination of any one or more of the carbons includes the forming material used to produce the connected microstructure 107F shown in FIG. 1F. In the example of FIG. 19A, a graphene-based sheet and/or structure containing sulfur entrainment and/or restriction 1902A with various thicknesses of 1904A and 1906A in various 3D cathode stent-type structures or configurations is shown. S includes the provision of required charge storage and resident in battery chemistries based on graphene. The required charge storage and resident are measured in milliampere hours. The synthesis of graphene-sulfur composite material with lightly oxidized graphene oxide sheet coated with poly(ethylene glycol) (PEG) coated sub-micron sulfur particles decorated with rice particles is described.

PEG及石墨烯塗層對於適應所塗佈硫粒子在放電期間之體積擴增、捕集可溶聚硫化物中間物且使得硫粒子導電具有重要性。所得石墨烯-硫複合物顯示在超過100個循環內至多

600 mAh/g之高且穩定比容量，表示用於具有高能量密度之可充電Li電池之有前景陰極材料。其他研究已顯示，已製造具有各種比表面積、孔隙體積以及平均孔隙尺寸之活化石墨烯(AG)且作為硫之基質施用。系統地研究AG孔隙結構參數及硫負載量對Li-硫電池之電化效能之影響。PEG and graphene coatings are important for adapting to the volume expansion of the coated sulfur particles during discharge, trapping soluble polysulfide intermediates, and making the sulfur particles conductive. The resulting graphene-sulfur composite shows at most in more than 100 cycles

The high and stable specific capacity of 600 mAh/g represents a promising cathode material for rechargeable Li batteries with high energy density. Other studies have shown that activated graphene (AG) with various specific surface areas, pore volumes, and average pore sizes has been manufactured and applied as a sulfur matrix. Systematically study the influence of AG pore structure parameters and sulfur loading on the electrochemical performance of Li-sulfur batteries.

結果顯示，電池之比容量、循環效能以及庫倫效率與孔隙結構及硫負載量緊密相關。具有72 wt.%之高硫負載量之AG3尺寸化(S)複合電極展現在1,000個循環內在50%容量保持率下之極佳長期循環穩定性及超低容量衰減速率(0.05%/個循環)。另外，當使用LiNO₃ 作為電解質添加劑時，AG3/S電極展現在1,000個循環內在~98%下之類似容量保持率及高庫倫效率。AG3/S電極系列之極佳電化效能係歸因於混合微孔/中孔結構、高表面積以及微孔/中孔內AG基質及良好分佈之硫之良好導電性，該良好導電性有益於循環期間電學及離子轉移。The results show that the specific capacity, cycle performance and coulombic efficiency of the battery are closely related to the pore structure and sulfur loading. The AG3 size (S) composite electrode with a high sulfur loading of 72 wt.% exhibits excellent long-term cycle stability and ultra-low capacity decay rate (0.05%/cycle) at a capacity retention rate of 50% within 1,000 cycles ). In addition, when using LiNO ₃ as an electrolyte additive, the AG3/S electrode exhibits a similar capacity retention rate and high coulombic efficiency at ~98% within 1,000 cycles. The excellent electrochemical performance of the AG3/S electrode series is attributed to the mixed microporous/mesoporous structure, high surface area, and the good conductivity of the AG matrix in the microporous/mesopore and the well-distributed sulfur, which is beneficial to circulation During the electrical and ion transfer.

圖19B顯示3D少層石墨烯陽極支架，諸如經製備以併於用於在石墨烯層之間具有Li間夾之Li離子或Li S系統陽極之形成材料內或用作其的碳支架300及/或鋰化碳支架400A。在圖19B之實例中，Li離子(Li+)係以各種組配1900B顯示，包括被間夾至FLG中1902B及Li金屬可逆包括於以碳為主之主體支架中1904B。向雙層石墨烯中之Li間夾可關於且解決以下：石墨烯之真實容量及石墨中之Li儲存方法，其呈現Li離子電池領域中之問題。19B shows a 3D few-layer graphene anode stent, such as a carbon stent 300 prepared and used as a Li ion or Li S system anode with Li sandwiched between graphene layers or used as a forming material. / Or lithiated carbon support 400A. In the example of FIG. 19B, Li ions (Li+) are shown in various configurations 1900B, including 1902B interposed in FLG and Li metal reversibly included in a carbon-based main frame 1904B. The intercalation of Li in double-layer graphene can be related to and solve the following: the true capacity of graphene and the storage method of Li in graphite, which present problems in the field of Li-ion batteries.

理論計算證實，分段鋰雙層石墨烯產品之各種生理化學表徵進一步顯露規則Li間夾現象且因此完全例示此基本二維鋰儲存模式。此等發現不僅用清晰鋰儲存方法使商業石墨成為第一電極，且亦引導Li離子電池中之石墨烯材料之發展。單層石墨烯及少層石墨烯中之Li吸收及間夾不同於散裝石墨相關聯之Li吸收及間夾。對於單層石墨烯，使用叢集擴增方法以系統地探索隨所吸收Li含量而變之最低能量離子組配。預測除非單層石墨烯表面包括缺陷，否則不存在使彼表面上之Li吸收穩定之Li佈置。根據此結果得出結論，與散裝石墨相比，缺陷不良單層石墨烯展現顯著較差之容量。Theoretical calculations confirmed that the various physiochemical characterizations of the segmented lithium double-layer graphene products further revealed the regular Li intercalation phenomenon and thus completely exemplified this basic two-dimensional lithium storage mode. These discoveries not only use clear lithium storage methods to make commercial graphite the first electrode, but also lead the development of graphene materials in Li-ion batteries. The Li absorption and intercalation in single-layer graphene and few-layer graphene are different from the Li absorption and intercalation associated with bulk graphite. For single-layer graphene, the cluster amplification method is used to systematically explore the lowest energy ion composition that varies with the absorbed Li content. It is predicted that unless the single-layer graphene surface includes defects, there will be no Li arrangement that stabilizes Li absorption on the other surface. Based on this result, it is concluded that the defective single-layer graphene exhibits a significantly poorer capacity compared to bulk graphite.

在一些實施方案中，除犧牲膜基體以及支撐膜基體中之任一者或多者之外，以碳為主之粒子膜可包括至少以下類粒子特性：基體之可調諧速度；自植入至吸附之可調諧衝擊能；可調諧厚度；以及可調諧孔隙度；以上特性中之任一者或多者可與附加型製造能力整合。In some embodiments, in addition to any one or more of the sacrificial film substrate and the supporting film substrate, the carbon-based particle film may include at least the following particle characteristics: tunable speed of the substrate; self-implantation to Tunable impact energy of adsorption; tunable thickness; and tunable porosity; any one or more of the above characteristics can be integrated with add-on manufacturing capabilities.

在一些實施方案中，如結合示於圖1A至圖1F中之元件實質上所論述，本發明所揭露之碳及以碳為主之結構中之任一者或多者可致能優於當前可獲得之Li離子及/或Li S電池之大量電池效能優勢，包括：以達成包括介於約400至650 (W·h)/kg範圍內且最大理論值為850 (W·h)/kg之能量密度且亦包括650 (MAh)/g之硫及/或硫間夾陰極態樣以及與其一起散佈以界定孔隙及/或空隙之石墨烯片102A及/或傳導性碳粒子態樣等的物理及/或電能儲存及/或傳導性值中之任一者或多者，在間夾於其中之離子Li (Li+)情況下最終達成900至2,000 (mAh)/g之能量密度儲存值。In some embodiments, as substantially discussed in conjunction with the elements shown in FIGS. 1A to 1F, any one or more of the carbon and carbon-based structures disclosed in the present invention may be superior to the current A large number of battery performance advantages of Li ion and/or Li S batteries are available, including: to achieve a maximum theoretical value of 850 (W·h)/kg in the range of about 400 to 650 (W·h)/kg The energy density also includes 650 (MAh)/g of sulfur and/or sulfur sandwiched between the cathode pattern and the graphene sheet 102A and/or conductive carbon particle pattern dispersed with it to define pores and/or voids. Any one or more of physical and/or electrical energy storage and/or conductivity values will eventually reach an energy density storage value of 900 to 2,000 (mAh)/g in the case of ions Li (Li+) sandwiched between them.

圖20A顯示循環內之陰極比容量位準及作為基於或使用以碳為主之粒子100A之系統之應用及/或使用代表的各種代表性硫奈米限制以及其衍生圖式及影像。各種組合物及/或化合物之如以mAh/g為單位所量測之改良式陰極比容量、電極位準示於圖2008a中，該等組合物及/或化合物中之任一者或多者至少部分包括形成有與其整合之s以增強陰極比容量之以碳為主之粒子100A。FIG. 20A shows the cathode specific capacity level in the cycle and various representative sulfur nanometer limits as well as their derivative schemes and images as representative of the application and/or use of a system based on or using carbon-based particles 100A. The specific capacity and electrode level of the modified cathode measured in mAh/g for various compositions and/or compounds are shown in Figure 2008a. Any one or more of these compositions and/or compounds At least part of it includes carbon-based particles 100A formed with integrated s to enhance the specific capacity of the cathode.

圖20B及20C顯示關於用於減少聚硫化物(PS)穿梭相關問題之加速碳調諧之圖表，該等圖表指示增加以碳為主之材料、以碳為主之粒子100A以及其變型之孔隙度減少PS穿梭，定義為在硫S到達負電極表面且經歷化學還原之情況下，導致不合需要之自動電化電池自放電。示於圖20B中之圖表2002B顯示一般處於比高孔隙度碳更高位準下之低孔隙度碳之平均強度變化。示於圖20C中之圖表2002C顯示相對於低孔隙度碳而言在重複電池使用循環內一般具有更高容量保持率百分比位準之高孔隙度碳。Figures 20B and 20C show graphs of accelerated carbon tuning used to reduce the problems associated with polysulfide (PS) shuttles. The graphs indicate the addition of carbon-based materials, carbon-based particles 100A, and the porosity of their variants. The reduction of PS shuttle is defined as the undesirable self-discharge of the automatic electrochemical battery when sulfur S reaches the surface of the negative electrode and undergoes chemical reduction. Graph 2002B shown in Figure 20B shows the average strength change of low-porosity carbon, which is generally at a higher level than high-porosity carbon. The graph 2002C shown in FIG. 20C shows that high-porosity carbon generally has a higher percentage level of capacity retention during repeated battery usage cycles relative to low-porosity carbon.

以碳為主之粒子100A調諧可達成包括以下之更高效製造：Li利用及電池電極內活性材料與非活性材料之比之潛在增大、黏合劑還原、均一性改進及受控電化反應，諸如電池導電性及/或活性。以碳為主之粒子100A之參數可經調諧以達成隨Li負載量百分比/單位以碳為主之粒子100A之面積或體積而變之特定效能特點，包括： ●            在小於容量之低負載位準下，補償第一電荷損失/更有效SEI形成；在飽和度/匹配負載量下，電流耦合至碳之富含Li之區域， ●            當與電解質接觸且經由石墨烯層之間之間夾來***Li及/或Li離子時，氧化材料； ●            將金屬Li以過量負載位準浸潤至經工程改造之主體碳中；組配主體以用以收納/穩定化Li擴增且抑制因Li表面積增加所致之樹枝狀結晶形成，使得比容量能夠與純Li相稱：＞ 2,000 mAh/g；以及 ●            製備可直接轉移至鋰離子混合電容器之Li離子方法(process/methodology)。100A tuning of carbon-based particles can achieve more efficient manufacturing including: Li utilization and potential increase in the ratio of active materials to inactive materials in battery electrodes, binder reduction, uniformity improvement, and controlled electrochemical reactions, such as Battery conductivity and/or activity. The parameters of the carbon-based particle 100A can be tuned to achieve specific performance characteristics that vary with the percentage of Li loading/unit of the area or volume of the carbon-based particle 100A, including: ● At a low load level less than the capacity, compensate for the first charge loss/more effective SEI formation; under saturation/matched load, the current is coupled to the carbon-rich Li-rich area, ● When in contact with the electrolyte and inserting Li and/or Li ions between the graphene layers, the material is oxidized; ● Infiltrate metallic Li into the engineered main carbon at an excessive loading level; assemble the main body to accommodate/stabilize Li amplification and inhibit the formation of dendrites due to the increase in Li surface area, so that the specific capacity can be Compatible with pure Li:> 2,000 mAh/g; and ● Preparation of Li-ion method (process/methodology) that can be directly transferred to lithium-ion hybrid capacitors.

如清單2900E中所概述之與Li及/或Li離子向諸如以碳為主之粒子100A之以碳為主之結構中之熱及/或液體灌注相關之持續挑戰可包括關於固體與液體電解質界面處之表面張力、潤濕性之Li反應性管理；毛細管Li及/或S浸潤動力學管理、通過電極厚度之電學梯度工程改造、使得Li在集電器處最高之Li浸潤及向電解質界面處之更高離子傳導濃度及/或位準之過渡之分級以及藉由促進與電解質接觸之穩定SEI形成且最小化與空氣反應性進行之表面化學性質之經謹慎調諧之工程改造。As outlined in Listing 2900E, ongoing challenges related to the thermal and/or liquid infusion of Li and/or Li ions into carbon-based structures such as carbon-based particles 100A may include the solid-liquid electrolyte interface Li reactivity management at the surface tension and wettability; capillary Li and/or S infiltration kinetics management, through the electrical gradient engineering of the electrode thickness, so that the highest Li infiltration at the current collector and at the electrolyte interface The classification of higher ion conduction concentrations and/or level transitions and carefully tuned engineering of surface chemistry by facilitating the formation of stable SEI in contact with the electrolyte and minimizing reactivity with air.

所揭露之態樣可在可類似於電鍍中之光亮劑之傳統二維(2D)鍍覆基礎上構建。在電鍍中，化學添加劑之添加可常常增加極化、減小電流密度；諸如再導引電流密度至如與諸如突起部分之高區域相對之低區域；產生相對高成核速率，且產生中等電荷轉移速率。在用以進行電池充電及放電循環之鍍覆或剝離之情形下，對於具有配備有如圖1A至圖1F中所示之以碳為主之粒子100A之電極之電池，碳膜可充當用於SEI形成以及再導引電流密度至如與高區域相對之低區域之可撓性載體。The disclosed aspect can be constructed on the basis of traditional two-dimensional (2D) plating that can be similar to brighteners in electroplating. In electroplating, the addition of chemical additives can often increase polarization and reduce current density; such as re-directing the current density to a low area such as a high area such as a protruding part; generating a relatively high nucleation rate and generating a medium charge Transfer rate. In the case of plating or peeling for battery charging and discharging cycles, for batteries with electrodes equipped with carbon-based particles 100A as shown in FIGS. 1A to 1F, the carbon film can be used for SEI Form and then guide the current density to a flexible carrier such as a low area as opposed to a high area.

在產生以碳為主之粒子100A且將其與Li離子電池整合之情形下用於本文中，膠結可用於所揭露之製造技術中之任一種或多種中。膠結意指藉由加熱與粉末狀固體接觸之金屬來更改金屬之方法，銅產生中之沈澱可指且/或可涉及非均相方法。此類方法可意指以下條件：其中反應物為諸如固體及氣體、固體及液體之二個或更多個相、二種不可混溶液體之組分；或其中一或多種反應物經歷界面處、固體催化劑表面上之化學變化；其中離子在固體金屬表面處還原至零價，諸如Fe粒子表面上之Cu離子；以及其中鐵氧化且銅還原，諸如與Li對C類似，銅在電流系列上相對較高。In the context of producing carbon-based particles 100A and integrating them with Li-ion batteries, cementing can be used in any one or more of the disclosed manufacturing techniques. Cementation refers to a method of modifying a metal by heating the metal in contact with a powdered solid. The precipitation in copper production may refer to and/or may involve a heterogeneous method. Such methods can mean the following conditions: where the reactants are components of two or more phases such as solid and gas, solid and liquid, two immiscible liquids; or where one or more reactants experience the interface , The chemical change on the surface of the solid catalyst; where the ions are reduced to zero valence at the surface of the solid metal, such as Cu ions on the surface of Fe particles; and where the iron is oxidized and the copper is reduced, such as Li vs. C, copper is on the current series Relatively high.

可管理包括Li金屬之熔融金屬之熔接以使得所提及技術中之任一種或多種可與以碳為主之粒子100A功能上整合且/或用於產生以碳為主之粒子100A以增強Li離子或Li S電池效能。該等輔助方法及/或技術包括：經由熔接進行之反應性金屬管理；用於利用惰性屏蔽氣體以經由液態金屬方法，諸如藉由熔接來接合諸如Ti及Al之反應性金屬的經典金屬惰性氣體(MIG)、亦稱為鎢惰性氣體(TIG)之氣體鎢電弧熔接(GTAW)以及經浸沒電弧熔接(SAW)。實例包括在無氧化之情況下使用惰性屏蔽氣體以形成反應性金屬之液體池，其中諸如TiO₂ 、Al2O₃ 之氧化物之△Gf與Li₂ O之△Gf同等位準。在存在反應性液體金屬之情況下經由在反應性金屬周圍受控使用惰性屏蔽氣體可有效地管理氧氣及濕度。在該等環境及條件中，可經由受控屏蔽氣體組配及操作將液體Li浸潤至以碳為主之粒子100A之以碳為主之結構中。The fusion of molten metal including Li metal can be managed so that any one or more of the mentioned technologies can be functionally integrated with carbon-based particles 100A and/or used to produce carbon-based particles 100A to enhance Li Ion or Li S battery performance. These auxiliary methods and/or technologies include: reactive metal management through welding; and classical metal inert gas for using inert shielding gas to join reactive metals such as Ti and Al through liquid metal methods, such as by welding (MIG), gas tungsten arc welding (GTAW), also known as tungsten inert gas (TIG), and submerged arc welding (SAW). Examples include the use of an inert non-oxidizing in the case where the shielding gas to form a pool of liquid reactive metals, wherein the TiO _2, △ Gf oxides of Al2O ₃ and Li △ Gf ₂ O as the same level. In the presence of reactive liquid metal, the controlled use of inert shielding gas around the reactive metal can effectively manage oxygen and humidity. In these environments and conditions, the liquid Li can be infiltrated into the carbon-based structure of the carbon-based particles 100A through the controlled shielding gas assembly and operation.

圖21顯示包括初始碳及N 摻雜碳製圖之3DN 摻雜FL石墨烯之拉曼光譜。在圖21之實例中，3DN 摻雜FL石墨烯2100之拉曼光譜包括在約2730 cm^-1 處之2D峰2102及分別在約1600 cm^-1 及1400 cm^-1 處之D峰2104、2106。Figure 21 shows the Raman spectrum of 3D N- doped FL graphene including initial carbon and N- doped carbon mapping. In the example of FIG. 21, 3D N doped FL Raman spectrum of the graphene comprises from about 2100 2730 cm 2D peak of 2102 ^{cm -1} and 1600 cm ^-1, respectively, and about 1400 cm D peak at 2104 ^{cm -1} in the, 2106.

圖22顯示與雙層石墨烯2200相關聯之各種特性。在圖22之實例中，樣品雙層石墨烯基礎結構2200顯示為具有定向於所示位置中之二層石墨烯，該位置理解為僅含有一個、二個或三個原子層之裝置。示意圖2202顯示個別石墨烯片之間之1.42 Å、1.94 Å及/或3.35 Å之大致間距量測結果。示意圖2204顯示可存在於邊緣平面之經界定鄰近區域內且/或輔助包括以碳為主之粒子結構之一或多個石墨烯片之產生的各種例示性缺陷性位點2206及/或2208。示意圖2210顯示硬球體碳粒子模型之俯視圖之各種模型圖2212。Figure 22 shows various characteristics associated with the double-layer graphene 2200. In the example of FIG. 22, the sample double-layer graphene base structure 2200 is shown as having two layers of graphene oriented in the position shown, which is understood to be a device containing only one, two, or three atomic layers. Diagram 2202 shows the approximate distance measurement results of 1.42 Å, 1.94 Å, and/or 3.35 Å between individual graphene sheets. The schematic diagram 2204 shows various exemplary defect sites 2206 and/or 2208 that may exist in the defined adjacent area of the edge plane and/or assist in the generation of one or more graphene sheets including a carbon-based particle structure. The schematic diagram 2210 shows various model diagrams 2212 of the top view of the hard sphere carbon particle model.

在一些實施方案中，可執行反應器調諧以例如進行以下中之任一者或多者：增大FL石墨烯間距、減小凡得瓦爾力；控制摻雜；促進碳空位形成；以及減少Li吸附能量及/或增加Li容量。Li離子間夾可例如在藉由經增大間距適應間夾之情況下將石墨烯片堆疊自A-B組配位移至A，其中例如在石墨中，A-A可在去間夾之情況下位移回至A-B；且在FL石墨烯中，在FL石墨烯中，AA堆疊在去間夾之情況下諸如藉由維持經增大間距而保留。該等堆疊組配可與示於圖1A至圖1F中之以碳為主之粒子100A相關聯。In some embodiments, reactor tuning may be performed, for example, to perform any one or more of the following: increasing FL graphene spacing, reducing Van der Waals force; controlling doping; promoting carbon vacancy formation; and reducing Li Absorb energy and/or increase Li capacity. The Li ion clamp can, for example, shift the graphene sheet stack from AB assembly to A by increasing the spacing to accommodate the clamp. For example, in graphite, AA can be moved back to A without the inter-clamping. AB; and in FL graphene, in FL graphene, the AA stack is retained without inter-pinching, such as by maintaining the increased spacing. These stacked configurations can be associated with the carbon-based particles 100A shown in FIGS. 1A to 1F.

圖23顯示用於描繪用以製備含有以碳為主之粒子之3D支架型膜之例示性操作2300之例示性流程圖。在圖23之實例中，方法3300包括藉由在操作2306時向卷軸式處理裝置或設備提供3D支架型膜來在操作2304時製備其中含有以碳為主之粒子之3D支架型膜。可在操作2308時將富含碳之電極沈積於3D支架型膜上；且不依賴於化學上非活性黏合材料之應用在卷軸式處理裝置或設備上處理3D支架型膜可在操作2312時之方法2300結束之前發生在操作2310時。Figure 23 shows an exemplary flow chart depicting an exemplary operation 2300 for preparing a 3D scaffold-type membrane containing carbon-based particles. In the example of FIG. 23, the method 3300 includes preparing a 3D stent-type film containing carbon-based particles in operation 2304 by providing a 3D stent-type film to the reel-type processing device or equipment in operation 2306. The carbon-rich electrode can be deposited on the 3D stent-type membrane in operation 2308; and does not rely on the application of chemically inactive adhesive materials. The 3D stent-type membrane can be processed on a reel processing device or equipment in operation 2312. It occurs at operation 2310 before the end of method 2300.

本揭露內容中所描述之主題之一個創新態樣可以鋰(Li)離子電池之形式實施，該Li離子電池包括陽極、與陽極相對定位之陰極、定位於陽極與陰極之間之多孔隔板以及與陽極及陰極接觸之液體電解質。陽極包括導電基體。第一膜沈積於導電基體上。第一膜包括第一濃度之經組配以界定第一膜之第一導電性的彼此接觸之碳粒子。碳粒子中之各者包括由少層石墨烯片形成之多個聚集體。形成多孔結構之多個聚集體經組配以經歷鋰化。An innovative aspect of the subject described in this disclosure can be implemented in the form of a lithium (Li) ion battery including an anode, a cathode positioned opposite to the anode, a porous separator positioned between the anode and the cathode, and Liquid electrolyte in contact with anode and cathode. The anode includes a conductive substrate. The first film is deposited on the conductive substrate. The first film includes a first concentration of carbon particles in contact with each other configured to define the first conductivity of the first film. Each of the carbon particles includes multiple aggregates formed of few-layer graphene sheets. The multiple aggregates forming the porous structure are assembled to undergo lithiation.

鋰化可包括間夾操作或鍍覆操作中之任一者或多者。陽極及陰極中之各者可包括電活性材料。多孔結構經組配以在少層石墨烯片之接觸點之間提供電傳導。多孔結構可經組配以含有熔融Li金屬。多孔結構可經組配以接納液體電解質，該液體電解質可經組配以促進多個Li離子在多孔結構內之運輸。The lithiation may include any one or more of a pinching operation or a plating operation. Each of the anode and cathode may include electroactive materials. The porous structure is configured to provide electrical conduction between the contact points of the few graphene sheets. The porous structure can be configured to contain molten Li metal. The porous structure can be configured to receive a liquid electrolyte, and the liquid electrolyte can be configured to facilitate the transportation of multiple Li ions within the porous structure.

第二膜可沈積於第一膜上。第二膜可包括第二濃度之以碳為主之粒子。第二濃度之以碳為主之粒子經組配以提供低於第一導電性之第二膜之第二導電性。電活性材料可駐存於陽極及陰極中之一者或二者之孔隙中。電活性材料之比表面積(SSA)可介於約1,635 m² /g與2,675 m² /g之間。電活性材料可包括以下中之任一者或多者：預鋰化少層石墨烯(FLG)片、初始石墨烯、氧化石墨烯、還原氧化石墨烯、氟化石墨烯、氯化石墨烯、溴化石墨烯、碘化石墨烯、氫化石墨烯、氮化石墨烯、硼摻雜石墨烯、氮摻雜石墨烯、化學官能化石墨烯、其物理或化學活化或蝕刻型式、硫摻雜石墨烯或其導電聚合物塗佈或接枝型式。The second film can be deposited on the first film. The second film may include a second concentration of carbon-based particles. The second concentration of carbon-based particles is assembled to provide a second conductivity lower than the first conductivity of the second film. The electroactive material may reside in the pores of one or both of the anode and the cathode. The specific surface area (SSA) of the electroactive material may be between about 1,635 m ² /g and 2,675 m ² /g. The electroactive material may include any one or more of the following: pre-lithiated few-layer graphene (FLG) sheets, initial graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, Brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, its physical or chemical activation or etching pattern, sulfur-doped graphene Coating or grafting type of olefin or its conductive polymer.

多孔結構可由不依賴於黏合劑之聚集體界定且經組配以成型為尺寸為介於1-30 μm範圍內、＜ 50 μm或高於500 nm中之任一者或多者之實質上球形形狀。多孔結構可包括經組配以併有矽(Si)之活性Li間夾結構。活性Li間夾結構之比容量可介於約730 - 3,600 mAh/g之間。化學官能化石墨烯可包括選自以下之官能基：醌、氫醌、四級銨化芳胺、硫醇、二硫化物、磺酸酯(- SO₃ )、過渡金屬氧化物、過渡金屬硫化物或其組合，以上物質包括經組配以與以下中之任一者或多者反應或併有以下中之任一者或多者之官能基：鎂(Mg)、鈣(Ca)、鋁(Al)、鍶(Sn)以及鋅(Zn)。The porous structure can be defined by aggregates that do not rely on binders and are assembled to be shaped into a substantially spherical shape with a size in the range of 1-30 μm, <50 μm or more than 500 nm. shape. The porous structure may include an active Li sandwich structure combined with silicon (Si). The specific capacity of the active Li sandwich structure can be between about 730-3,600 mAh/g. Chemically functionalized graphene may include functional groups selected from the group consisting of: quinone, hydroquinone, quaternary ammonium arylamine, mercaptan, disulfide, sulfonate (-SO ₃ ), transition metal oxide, transition metal sulfide The above substances include functional groups that are formulated to react with any one or more of the following or have any one or more of the following: magnesium (Mg), calcium (Ca), aluminum (Al), Strontium (Sn), and Zinc (Zn).

導電基體可為集電器，該集電器可至少部分以發泡體為主或衍生於發泡體且選自以下中之任一者或多者：金屬發泡體、金屬網、金屬篩網、穿孔金屬、以片材為主之3D結構、金屬纖維墊、金屬奈米線墊、導電聚合物奈米纖維墊、導電聚合物發泡體、導電聚合物塗佈的纖維發泡體、碳發泡體、石墨發泡體、碳氣凝膠、碳乾凝膠、石墨烯發泡體、氧化石墨烯發泡體、還原氧化石墨烯發泡體、碳纖維發泡體、石墨纖維發泡體以及剝離型石墨發泡體。The conductive matrix may be a current collector, which may be at least partially foam-based or derived from foam and selected from any one or more of the following: metal foam, metal mesh, metal mesh, Perforated metal, sheet-based 3D structure, metal fiber mat, metal nanowire mat, conductive polymer nanofiber mat, conductive polymer foam, conductive polymer coated fiber foam, carbon hair Foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, and Exfoliated graphite foam.

集電器可成型為箔。電活性材料可包括以下中之一或多者：無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片。無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片可選自硒化鉍或碲化鉍、過渡金屬二硫屬化物或三硫屬化物、過渡金屬硫化物、硒化物或碲化物、氮化硼或其組合，其中奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片之厚度小於100 nm。The current collector can be shaped as a foil. The electroactive material may include one or more of the following: inorganic materials, nano particles, nano disks, nano flakes, nano coatings or nano flakes. Nanoparticles, nanoplates, nanosheets, nano coatings or nanosheets of inorganic materials can be selected from bismuth selenide or bismuth telluride, transition metal dichalcogenides or trichalcogenides, transition metal sulfides, Selenide or telluride, boron nitride or a combination thereof, wherein the thickness of the nanoparticle, nanodisk, nanosheet, nano coating or nanosheet is less than 100 nm.

本揭露內容中所描述之主題之另一創新態樣可以電化電池電極之形式實施，該電化電池電極包括沈積於導電基體上之膜層。膜層包括一定濃度之由正交熔合在一起之多個少層石墨烯片形成之碳聚集體及由多個少層石墨烯片界定之多孔結構。多孔結構經組配以在多個少層石墨烯片中之任二個或更多個之間之接觸點之間提供電傳導或容納電活性材料中的任一者或多者。Another innovative aspect of the subject described in this disclosure can be implemented in the form of an electrochemical cell electrode, which includes a film layer deposited on a conductive substrate. The film layer includes a certain concentration of carbon aggregates formed by orthogonally fused together a plurality of few-layer graphene sheets and a porous structure defined by a plurality of few-layer graphene sheets. The porous structure is configured to provide electrical conduction or contain any one or more of the electroactive materials between the contact points between any two or more of the plurality of few-layer graphene sheets.

多個少層石墨烯片之一或多對鄰接石墨烯片可包括藉由3Å至20Å之D-間距間隔開之第一石墨烯片及第二石墨烯片。電化電池電極可包含陽極，其中電活性材料包括散佈於陽極中之D-間距中之元素鋰(Li)。多個Li離子由元素Li提供。One or more pairs of adjacent graphene sheets of the plurality of few-layer graphene sheets may include a first graphene sheet and a second graphene sheet separated by a D-spacing of 3 Å to 20 Å. The electrode of an electrochemical cell may include an anode, wherein the electroactive material includes the element lithium (Li) dispersed in the D-spacing in the anode. Multiple Li ions are provided by the element Li.

額外膜沈積於該膜上。該膜經組配以提供第一導電性且額外膜經組配以提供不同於第一導電性之第二導電性。An additional film is deposited on the film. The film is configured to provide a first conductivity and the additional film is configured to provide a second conductivity different from the first conductivity.

多孔結構可包括經組配以被液相電解質浸潤之多個互連通道。第一導電性及第二導電性均可與液相電解質中由電活性材料提供之多個Li離子之遷移成正比。遷移可朝向與電化電池電極實質上相對定位之額外電化電池電極。多個互連通道可經組配以防止電化電池電極或額外電化電池電極中之任一者或多者上之Li離子積聚。The porous structure may include a plurality of interconnected channels configured to be infiltrated by the liquid electrolyte. Both the first conductivity and the second conductivity are proportional to the migration of multiple Li ions provided by the electroactive material in the liquid electrolyte. Migration may be towards additional electrochemical cell electrodes positioned substantially opposite to the electrochemical cell electrodes. Multiple interconnecting channels can be configured to prevent the accumulation of Li ions on any one or more of the electrode of the electrochemical cell or the electrode of the additional electrochemical cell.

多孔結構可包括中尺度建構或微米尺度碎形建構中之任一者或多者。電活性材料可包括可經組配以被灌注至多孔結構中之熔融Li金屬。The porous structure may include any one or more of a mesoscale structure or a microscale fractal structure. The electroactive material can include molten Li metal that can be configured to be poured into the porous structure.

多孔結構可經組配以被電解質浸潤，該電解質可經組配以運輸Li離子。多孔結構可經組配以被於液相或凝膠相中之任一者或多者中之電解質浸潤。電解質可處於聚合物相或實質上固體電解質中間相中之任一者或多者中，該實質上固體電解質中間相可包括固態電解質，該固態電解質可經組配以至少實質上防止或減少Li樹枝狀結晶形成、短路形成或固態電解質滲漏中之任一者或多者。The porous structure can be configured to be infiltrated by an electrolyte, and the electrolyte can be configured to transport Li ions. The porous structure may be configured to be infiltrated by the electrolyte in any one or more of the liquid phase or the gel phase. The electrolyte may be in any one or more of a polymer phase or a substantially solid electrolyte intermediate phase. The substantially solid electrolyte intermediate phase may include a solid electrolyte, which may be configured to at least substantially prevent or reduce Li Any one or more of dendritic crystal formation, short circuit formation, or solid electrolyte leakage.

固態電解質可選自固體聚合物電解質、凝膠聚合物電解質或非聚合物電解質中之任一者或多者。固態電解質可包括溶解於聚合物主體中之Li鹽，該聚合物主體可包括以下中之任一者或多者：聚乙二醇(PEO)、聚偏二氟乙烯(polyvinylidene fluoride/polyvinylidene difluoride，PVDF)、聚(對苯醚) (PPO)或聚、聚(偏二氟乙烯-共-六氟丙烯) (PVDF-HFP)、聚(甲基丙烯酸甲酯) (PMMA)、聚苯乙烯磺酸酯(PSS)及此等聚合物之鹽(Li或Na鹽)、PAN、PANI。The solid electrolyte may be selected from any one or more of solid polymer electrolytes, gel polymer electrolytes, and non-polymer electrolytes. The solid electrolyte may include Li salt dissolved in a polymer body, and the polymer body may include any one or more of the following: polyethylene glycol (PEO), polyvinylidene fluoride/polyvinylidene difluoride, PVDF), poly(p-phenylene ether) (PPO) or poly, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(methyl methacrylate) (PMMA), polystyrene sulfonate Acid ester (PSS) and the salt of these polymers (Li or Na salt), PAN, PANI.

實質上固體電解質中間相可包括於聚合物基質中捕集之液體組分或非聚合物固體電解質中之一者或另一者。液體組分經組配以促進Li離子運輸。非聚合物固體電解質可包括以下中之任一者或多者：實質上陶瓷材料或Li超離子導體(LISICON)、包括石榴石型Li₇ La₃ Zr₂ O₁₂ (LLZO)之併有陶瓷奈米纖維之複合材料、包括鈣鈦礦由鈦酸鈣構成之氧化鈣鈦礦物。非聚合物固體電解質之厚度可介於約0.5 μm至40 μm範圍內。厚度可經組配以實質上防止Li樹枝狀結晶形成或生長中之任一者或多者。The substantially solid electrolyte intermediate phase may include one or the other of a liquid component trapped in a polymer matrix or a non-polymer solid electrolyte. The liquid components are formulated to promote Li ion transport. The non-polymer solid electrolyte may include any one or more of the following: essentially ceramic materials or Li super ionic conductors (LISICON), including garnet-type Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) and ceramics The composite material of rice fiber, including perovskite is perovskite mineral composed of calcium titanate. The thickness of the non-polymer solid electrolyte may range from about 0.5 μm to 40 μm. The thickness can be configured to substantially prevent any one or more of the formation or growth of Li dendrites.

多孔結構中之通道可包括經組配以提供Li離子管道之第一部分、經組配以促進快速Li離子運輸之第二部分以及經組配以限制電活性材料之第三部分。導電性介於約1,000 S/m與約20,000 S/m之間之範圍內。The channels in the porous structure may include a first part configured to provide Li ion channels, a second part configured to promote rapid Li ion transport, and a third part configured to confine the electroactive material. The conductivity is in the range between about 1,000 S/m and about 20,000 S/m.

一或多個額外膜層可沈積於該膜層上，該一或多個額外膜層中之任一個或多個經組配以提供相對於緊接在前之膜層而言在與導電基體實質上正交之方向成比例地降低之導電性。One or more additional film layers may be deposited on the film layer, and any one or more of the one or more additional film layers are configured to provide a conductive substrate with respect to the immediately preceding film layer. The substantially orthogonal directions decrease the conductivity proportionally.

固體-電解質界面(SEI)可形成於多孔結構之鄰近區域內。電化電池可進一步包含定位於多孔結構之鄰近區域內之人工固體-電解質界面(ASEI)。ASEI在多孔結構形成期間原位形成或異地形成為塗層、膜或反應物中之任一者或多者。The solid-electrolyte interface (SEI) can be formed in the vicinity of the porous structure. The electrochemical cell may further include an artificial solid-electrolyte interface (ASEI) positioned in the vicinity of the porous structure. ASEI is formed in situ or heterogeneously formed as any one or more of coatings, membranes, or reactants during the formation of the porous structure.

多孔結構可包括可經組配以提供Li吸附中心之一或多個親鋰官能化表面。The porous structure can include one or more lithium-philic functionalized surfaces that can be configured to provide Li adsorption centers.

本揭露內容中所描述之主題之一個創新態樣可以製造陽極之方法之形式實施。該方法可包括以第一濃度位準成核多個碳粒子，基於第一濃度位準在犧牲基體上形成第一膜，碳粒子中之各者利用由熔合在一起之少層石墨烯片形成之多個聚集體界定，基於少層石墨烯片界定多孔結構，及將熔融鋰(Li)金屬灌注至多孔結構中。An innovative aspect of the subject described in this disclosure can be implemented in the form of a method of manufacturing anodes. The method may include nucleating a plurality of carbon particles at a first concentration level, forming a first film on the sacrificial substrate based on the first concentration level, and each of the carbon particles is formed by using a few layers of graphene sheets fused together The multiple aggregates are defined, based on a few graphene sheets to define a porous structure, and molten lithium (Li) metal is poured into the porous structure.

多個互連多孔通道可基於多個碳粒子來加以界定。第二膜可藉由在第一膜上以第二濃度位準成核碳粒子來形成。第一膜可經組配以提供第一導電性且第二膜可經組配以提供不同於第一導電性之第二導電性。第二導電性可低於第一導電性。The plurality of interconnected porous channels may be defined based on the plurality of carbon particles. The second film can be formed by nucleating carbon particles at a second concentration level on the first film. The first film may be configured to provide a first conductivity and the second film may be configured to provide a second conductivity different from the first conductivity. The second conductivity may be lower than the first conductivity.

第一膜之平均厚度可介於約10 µm與約200 µm之間之範圍內。碳粒子可在卷軸式處理設備上生長。該方法可包括以下中之任一者或多者：將熔融Li金屬氣化至金屬箔上以及將熔融Li金屬自金屬箔捲至多孔結構中。該方法可包括以下中之任一者或多者：製備陽極以與藉由化學官能化或硫化中之任一者或多者製備之陰極一起參與Li離子之可逆遷移以及在多孔結構上使多個石墨烯薄片緻密。The average thickness of the first film may be in the range between about 10 µm and about 200 µm. Carbon particles can be grown on reel-type processing equipment. The method may include any one or more of the following: vaporizing molten Li metal onto the metal foil and rolling the molten Li metal from the metal foil into the porous structure. The method may include any one or more of the following: preparing an anode to participate in the reversible migration of Li ions together with a cathode prepared by any one or more of chemical functionalization or sulfidation, and making a more porous structure. The graphene flakes are dense.

本揭露內容中所描述之主題之另一態樣可以用於產生鋰(Li)離子電池陽極之方法之形式實施。該方法可包括在基體上沈積第一多個碳粒子以及形成經組配以基於第一多個碳粒子提供第一導電性之第一膜。第一多個碳粒子中之各碳粒子可包括由正交熔合在一起之少層石墨烯片形成且經組配以界定多孔結構之多個3D聚集體。多孔配置形成於多孔結構中。將熔融Li金屬灌注至多孔結構中。該方法可包括以下中之任一者或多者：在第一膜上沈積第二多個碳粒子以及形成經組配以基於第二多個碳粒子提供第一導電性之第二膜。Another aspect of the subject matter described in this disclosure can be implemented in the form of a method for producing lithium (Li) ion battery anodes. The method may include depositing a first plurality of carbon particles on a substrate and forming a first film configured to provide a first conductivity based on the first plurality of carbon particles. Each of the carbon particles in the first plurality of carbon particles may include a plurality of 3D aggregates formed of a few graphene sheets orthogonally fused together and assembled to define a porous structure. The porous configuration is formed in the porous structure. The molten Li metal is poured into the porous structure. The method may include any one or more of the following: depositing a second plurality of carbon particles on the first film and forming a second film configured to provide a first conductivity based on the second plurality of carbon particles.

熔融Li金屬之灌注速率可基於熔融Li金屬之黏性阻力來進行選擇。熔融Li金屬可經組配以與第一多個碳粒子中之任一個或多個反應來產生碳化物。該方法可包括以下中之任一者或多者：將於氣相中之熔融Li金屬浸潤至多孔結構中，在由熔融Li金屬提供之任一個或多個Li離子與多孔結構之一或多個暴露表面之間引發化學反應，以及由一或多個暴露表面形成一或多個親鋰表面。The infusion rate of the molten Li metal can be selected based on the viscosity resistance of the molten Li metal. The molten Li metal can be configured to react with any one or more of the first plurality of carbon particles to produce carbides. The method may include any one or more of the following: infiltrating the molten Li metal in the gas phase into the porous structure, and one or more of any one or more Li ions provided by the molten Li metal and the porous structure. A chemical reaction is initiated between the two exposed surfaces, and one or more lithium-philic surfaces are formed from the one or more exposed surfaces.

該方法可包括用包括鹵素或金屬氧化物中之任一者或多者之活性元素塗佈親鋰表面中之任一個或多個。該方法可包括用具有低於Li之表面能之任一個或多個元素塗佈親鋰表面中之任一個或多個以及用具有低於Li之表面能之任一個或多個元素促進親鋰表面中之任一個或多個之Li潤濕增強。The method may include coating any one or more of the lithium-philic surfaces with active elements including any one or more of halogens or metal oxides. The method may include coating any one or more of the lithium-philic surface with any one or more elements having a surface energy lower than Li and promoting the lithium-philic surface with any one or more elements having a surface energy lower than Li Li wetting of any one or more of the surfaces is enhanced.

該方法可包括藉由將金屬粉末或包括碳化矽(SiC)之含金屬化合物中之任一者或多者併入碳預形成物中來產生黏合劑。Li潤濕可包括對界面表面張力進行工程改造。在一些態樣中，Li潤濕包含Li界面及多孔結構之暴露表面處之一或多個化學反應。Li潤濕增強可包括以下中之任一者或多者：在界面處添加一定量之摻雜劑以及影響對應於該量摻雜劑之Li潤濕之程度。可在多孔結構之一或多個暴露表面中之任一個處控制羥基(OH)吸附。The method may include generating a binder by incorporating any one or more of metal powder or a metal-containing compound including silicon carbide (SiC) into a carbon preform. Li wetting can include engineering the interfacial surface tension. In some aspects, Li wetting includes one or more chemical reactions at the Li interface and the exposed surface of the porous structure. Li wetting enhancement may include any one or more of the following: adding a certain amount of dopant at the interface and affecting the degree of Li wetting corresponding to the amount of dopant. The adsorption of hydroxyl (OH) can be controlled at any of one or more exposed surfaces of the porous structure.

在前述說明書中，已參照具體實例描述本揭露內容。然而，顯而易見地，在不脫離本揭露內容之較寬精神及範疇之情況下可對其作出各種修改及改變。舉例而言，參照方法動作之特別排序描述上文所描述之處理流程。然而，可在不影響本揭露內容之範疇或操作之情況下改變許多所描述方法動作之排序。本說明書及圖式應在例示性意義上而非在限制性意義上被看待。In the foregoing specification, the present disclosure has been described with reference to specific examples. However, it is obvious that various modifications and changes can be made to it without departing from the broader spirit and scope of the content of this disclosure. For example, the processing flow described above is described with reference to a special order of method actions. However, the sequence of actions of many described methods can be changed without affecting the scope or operation of the content of the disclosure. This description and the drawings should be viewed in an illustrative sense rather than a restrictive sense.

100,302:以碳為主之粒子 100A,302B:以碳為主之粒子,傳導性粒子 100E:以碳為主之粒子,中孔粒子 100F:階層式多孔網狀結構 100G:PS化合物,示意圖 101A:階層式孔隙,互連階層式孔隙 101B:互連3D黏聚體,石墨烯片,黏聚體,石墨烯片之導電互連黏聚體,石墨烯片之3D束,石墨烯片之互連3D束 101C:石墨烯片,水平堆疊組配 101F:尺寸 102:石墨烯片之互連3D束 102A:開放多孔支架 103F:尺寸,微孔織構,孔隙 104:傳導碳粒子 105,102F,104F,105F,1710A:孔隙 106F,507,1308,1310:路徑 107:相連路徑 107F:相連微結構,相連路徑 109F:擴散路徑 200,100D,1800E,1800A,1800B,1800C,1800D,1800E:顯微圖 201A:大孔隙 202:大孔隙或微孔隙 300B:碳支架,以碳為主之支架 300:碳支架,環狀碳支架 304:較小碳粒子 306:犧牲基體 400A:鋰化碳支架,以碳為主之粒子,鋰化以碳為主之支架,碳支架 402A:傳導性粒子,互連以碳為主之粒子,以碳為主之粒子 406A:膜層,中間層,層,單獨沈積層 408A,410A,412A:膜層,層,單獨沈積層 414A:電解質 416A,1704A:空隙 418A:鈍化層 420A:集電器 400B:電漿噴射炬系統,卷軸式(R2R)系統 402B:犧牲層 404B:犧牲層,最初層 406B,408B,410B:後續層 412B:原料供應管線 414B:電漿噴射炬,噴炬 416B,418B,420B:電漿噴射炬 422B,424B,426B,428B:噴射,電漿噴射炬 426,459,462,486,487,401:系列 430B,432B:方向 434B,439B:輪及/或卷軸 436B:向前運動,碳支架 440B:R2R處理設備 442B:層 444B:群組 500:二次電化電池系統,二次電化電池 501:陽極 502:陰極 505:解離Li離子傳導鹽,Li離子傳導鹽,Li離子 506,511:電子 508:放電 509:碳粒子 512,1306:Li離子 513,516:放大區域 514:熔融Li金屬 515:少層石墨烯片 517:隔板 518:Li離子傳導電解質溶液,電解質溶液,電解質 600A:碳材料 601A:暴露電極表面,電極表面 602A:特定元素 600B1:化學非反應性系統 600B2:化學反應性系統 700:浸潤過程工作流程示意圖 702:封裝碳支架,碳支架,以碳為主之支架 704,706:Li金屬,熔融Li金屬 708:鋰化碳化合物 800A:沃什伯恩方程式 800B:非反應性系統 802B:非潤濕組配 804B:自發潤濕組配,不可潤濕表面層組配 806B:以碳為主之支架 800C:反應性系統 802C:可潤濕反應性產物層組配 806C,808C:3D層 900:流程圖 902,904,906,1002A,1004A,1006A,1002B,1004B,1006B,1002C,1004C,1006C,1002D,1004D,1002,1002E,1004E,1002G,1002H,1002I,1004I,1006I,1008I,1002J,1004J,1002K,1004K,1006K,1002L,1002M,1004M,1002N,1002O,1004O,1002P,1102A,1104A,1106A,1108A,1102B,1104B,1106B,1102C,1104C,1106C,1202,1204,1206,1208,1210,1212:區塊 1000A,1000B,1000C,1000D,1000E,1000F,1000G,1000H,1000I,1000J,1000K,1000L,1000M,1000N,1000O,1000P,1100A,1100B,1100C,1200:方法 1300:陽極,理想化陽極 1302:3D以石墨烯為主之奈米結構 1304:黏合劑 1312:金屬摻雜劑 1314:石墨烯 1316:經表面活化擴散路徑 1500:理想化陰極組配 1600:原位3D奈米結構化少層石墨烯材料 1602:少層石墨烯片堆疊,少層石墨烯片之經Li浸潤堆疊 1604:Li源 1700A:部分 1702A:個別紐帶 1708A:表面 1900A:示意性描繪 1900B:組配 1902A:硫夾帶及/或限制 1902B:被間夾至FLG中 1904A,1906A:厚度 1904B:Li金屬可逆包括於以碳為主之主體支架中 2008A:圖 2002B,2002C:圖表 2100:3DN 摻雜FL石墨烯 2102:2D峰 2104,2106:D峰 2200:雙層石墨烯,雙層石墨烯基礎結構 2202,2204,2210:示意圖 2206,2208:缺陷性位點 2212:模型圖 2300,2304,2306,2308:操作 A:豎直高度方向 L:液相Li層 S:固體碳表面 V:黏性摩擦 θ:接觸角100,302: carbon-based particles 100A, 302B: carbon-based particles, conductive particles 100E: carbon-based particles, mesoporous particles 100F: hierarchical porous network structure 100G: PS compound, schematic 101A: Hierarchical pores, interconnected hierarchical pores 101B: interconnecting 3D cohesives, graphene sheets, cohesives, conductive interconnecting cohesives of graphene sheets, 3D bundles of graphene sheets, interconnection of graphene sheets 3D beam 101C: graphene sheets, horizontal stacking assembly 101F: size 102: interconnection of graphene sheets 3D beam 102A: open porous scaffold 103F: size, microporous texture, pore 104: conductive carbon particles 105, 102F, 104F, 105F, 1710A: Pores 106F, 507, 1308, 1310: Path 107: Connected path 107F: Connected microstructure, connected path 109F: Diffusion path 200, 100D, 1800E, 1800A, 1800B, 1800C, 1800D, 1800E: Micrograph 201A: Macropore 202: Macropore or micropore 300B: Carbon scaffold, mainly carbon scaffold 300: Carbon scaffold, ring carbon scaffold 304: Smaller carbon particles 306: Sacrificial matrix 400A: Lithium carbon scaffold, mainly carbon The particles, lithiated carbon-based scaffold, carbon scaffold 402A: conductive particles, interconnecting carbon-based particles, carbon-based particles 406A: film layer, intermediate layer, layer, separate deposition layer 408A, 410A, 412A: film, layer, separate deposition layer 414A: electrolyte 416A, 1704A: void 418A: passivation layer 420A: current collector 400B: plasma jet torch system, reel (R2R) system 402B: sacrificial layer 404B: sacrificial layer , The first layer 406B, 408B, 410B: the subsequent layer 412B: raw material supply line 414B: plasma jet torch, torch 416B, 418B, 420B: plasma jet torch 422B, 424B, 426B, 428B: jet, plasma jet torch 426,459,462,486,487,401 : Series 430B, 432B: direction 434B, 439B: wheel and/or reel 436B: forward movement, carbon bracket 440B: R2R processing equipment 442B: layer 444B: group 500: secondary electrochemical battery system, secondary electrochemical battery 501: Anode 502: Cathode 505: Dissociated Li ion conductive salt, Li ion conductive salt, Li ion 506, 511: Electron 508: Discharge 509: Carbon particles 512, 1306: Li ion 513, 516: Enlarged area 514: Molten Li metal 515: Few layers of graphene Sheet 517: separator 518: Li ion conductive electrolyte solution, electrolyte solution, electrolyte 600A: carbon material 601A: exposed electrode surface, electrode surface 602A: specific element 600B1: chemically non-reactive system 600B2: chemically reactive System 700: Schematic diagram of the work flow of the infiltration process 702: Encapsulated carbon support, carbon support, carbon-based support 704, 706: Li metal, molten Li metal 708: lithiated carbon compound 800A: Washburn equation 800B: non-reactive system 802B: non-wetting combination 804B: spontaneous wetting combination, non-wettable surface layer combination 806B: carbon-based bracket 800C: reactive system 802C: wettable reactive product layer combination 806C, 808C: 3D layer 900: flowcharts 902, 904, 906, 1002A, 1004A, 1006A, 1002B, 1004B, 1006B, 1002C, 1004C, 1006C, 1002D, 1004D, 1002, 1002E, 1004E, 1002G, 1002H, 1002I, 1004I, 1006I, 1008I, 1002J, 1004J, 1002K, 1004K, 1006K, 1002L, 1002M, 1004M, 1002N, 1002O, 1004O, 1002P, 1102A, 1104A, 1106A, 1108A, 1102B, 1104B, 1106B, 1102C, 1104C, 1106C, 1202, 1204, 1206, 1208, 1210, 1212: Block 1000A, 1000B, 1000C, 1000D, 1000E, 1000F, 1000G, 1000H, 1000I, 1000J, 1000K, 1000L, 1000M, 1000N, 1000O, 1000P, 1100A, 1100B, 1100C, 1200: Method 1300: Anode , Idealized anode 1302: 3D graphene-based nanostructure 1304: Adhesive 1312: Metal dopant 1314: Graphene 1316: Surface activated diffusion path 1500: Idealized cathode assembly 1600: In-situ 3D nanostructure Rice structured few-layer graphene material 1602: few-layer graphene sheet stack, Li-infiltrated stack of few-layer graphene sheet 1604: Li source 1700A: part 1702A: individual tie 1708A: surface 1900A: schematic depiction 1900B: assembly 1902A: Sulfur entrainment and/or restriction 1902B: Interposed into FLG 1904A, 1906A: Thickness 1904B: Li metal is reversibly included in a carbon-based main frame 2008A: Figure 2002B, 2002C: Figure 2100: 3D N doping FL graphene 2102: 2D peak 2104, 2106: D peak 2200: double-layer graphene, double-layer graphene base structure 2202, 2204, 2210: schematic diagram 2206, 2208: defect site 2212: model diagram 2300, 2304, 2306 , 2308: Operation A: Vertical height direction L: Liquid phase L i layer S: solid carbon surface V: viscous friction θ: contact angle

本揭露內容中所描述之主題之細節闡述於隨附圖式及以下描述中。主題之其他特點、態樣以及優點將自描述、圖式以及申請專利範圍變得顯而易見。The details of the subject described in this disclosure are described in the accompanying drawings and the following description. Other features, aspects, and advantages of the theme will become obvious from the description, diagrams, and scope of patent applications.

圖1A至圖1F顯示具有用於電傳導及離子運輸之各種經界定區域之以碳為主之粒子的圖式。Figures 1A to 1F show diagrams of carbon-based particles with various defined regions for electrical conduction and ion transport.

圖1H及1I顯示碳晶格及結構中Li離子之置放及/或間夾之示意圖。Figures 1H and 1I show schematic diagrams of the placement and/or intervening of Li ions in the carbon lattice and structure.

圖2顯示形成為深度延伸至若干鄰接堆疊FL石墨烯層中之空腔之示意圖。FIG. 2 shows a schematic diagram of a cavity formed to extend to a depth of several adjacent stacked FL graphene layers.

圖3顯示多層以碳為主之支架型結構之示意圖。Figure 3 shows a schematic diagram of a multi-layer carbon-based scaffold structure.

圖4A顯示具有於其中之被灌注至奈米尺度間隙中之鋰(Li)金屬之圖3中所示之結構的示意圖。FIG. 4A shows a schematic diagram of the structure shown in FIG. 3 with lithium (Li) metal impregnated into the nano-scale gap therein.

圖4B顯示以連續順序定位於卷軸式(R2R)處理設備上方之一系列電漿噴射炬之示意圖。Figure 4B shows a schematic diagram of a series of plasma jet torches positioned above the reel type (R2R) processing equipment in a continuous sequence.

圖5顯示例示性Li離子或Li S電化電池之示意圖。Figure 5 shows a schematic diagram of an exemplary Li ion or Li S electrochemical cell.

圖6A顯示向碳粒子中併入金屬粉末以進行Li潤濕及浸潤之示意圖。Fig. 6A shows a schematic diagram of incorporating metal powder into carbon particles for Li wetting and infiltration.

圖6B及6C分別顯示化學非反應性系統及化學反應性系統之示意圖。Figures 6B and 6C show schematic diagrams of a chemically non-reactive system and a chemically reactive system, respectively.

圖7顯示例示性方法工作流，其中熔融Li金屬被浸潤至碳黏聚體之間之空隙空間中。Figure 7 shows an exemplary method workflow in which molten Li metal is infiltrated into the void spaces between carbon aggregates.

圖8A顯示以碳為主之結構之浸潤速率之方程式。Figure 8A shows the equation for the wetting rate of carbon-based structures.

圖8B及8C顯示關於向碳結構中之Li浸潤之非反應性系統及反應性系統。Figures 8B and 8C show the non-reactive system and the reactive system regarding Li infiltration into the carbon structure.

圖9顯示描繪鋰化及合金化以碳為主之結構之例示性操作之流程圖。Figure 9 shows a flowchart depicting an exemplary operation of lithiation and alloying of a carbon-based structure.

圖10A顯示描繪製備以碳為主之結構之例示性操作之流程圖。Figure 10A shows a flow chart depicting an exemplary operation for preparing a carbon-based structure.

圖10B顯示描繪製備Li材料之例示性操作之流程圖。Figure 10B shows a flow chart depicting an exemplary operation for preparing Li material.

圖10C至圖10P顯示描繪製造電化電池電極之例示性操作之流程圖。10C to 10P show a flowchart depicting an exemplary operation for manufacturing an electrode of an electrochemical cell.

圖11A至11C顯示描繪製備碳粒子以進行鋰化之例示性操作。11A to 11C show exemplary operations depicting the preparation of carbon particles for lithiation.

圖12顯示描繪執行碳粒子之Li灌注之例示性操作之流程圖。Figure 12 shows a flow chart depicting an exemplary operation for performing Li pouring of carbon particles.

圖13顯示陽極示意圖。Figure 13 shows a schematic diagram of the anode.

圖14顯示在多個使用循環內之矽及碳陽極效能。Figure 14 shows the performance of silicon and carbon anodes over multiple cycles of use.

圖15及16顯示具有分散於其中之含硫化鋰(Li₂ S)奈米粒子之石墨烯之理想化陰極組配相關示意圖。Figures 15 and 16 show schematic diagrams related to the idealized cathode configuration of graphene _{with lithium sulfide (Li 2 S) nanoparticles dispersed therein.}

圖17A及17B顯示圖1A至1F之以碳為主之粒子之經放大部分。Figures 17A and 17B show enlarged parts of the carbon-based particles of Figures 1A to 1F.

圖18A至18E為碳粒子部分之顯微圖。Figures 18A to 18E are micrographs of the carbon particles.

圖19A顯示3D以碳為主之陰極之示意圖。Figure 19A shows a 3D schematic diagram of a carbon-based cathode.

圖19B顯示3D以碳為主之陽極之示意圖。Figure 19B shows a schematic diagram of a 3D carbon-based anode.

圖20A顯示例示性Li S電化電池之放電及充電循環。Figure 20A shows the discharge and charge cycles of an exemplary LiS electrochemical cell.

圖20B及20C顯示配備有包括碳之電極之電池之電池效能圖表。Figures 20B and 20C show battery performance graphs for batteries equipped with electrodes including carbon.

圖21顯示3DN 摻雜FL石墨烯之拉曼光譜(Raman spectra)。Figure 21 shows the Raman spectra of 3D N-doped FL graphene.

圖22顯示雙層石墨烯示意圖。Figure 22 shows a schematic diagram of double-layer graphene.

圖23顯示用於製備3D支架型膜之方法。Figure 23 shows a method for preparing a 3D stent-type membrane.

各個圖式中相同參考數字及名稱均指示相同元件。The same reference numbers and names in each drawing indicate the same elements.

300:碳支架，環狀碳支架 300: Carbon bracket, ring carbon bracket

302:以碳為主之粒子 302: Carbon-based particles

304:較小碳粒子 304: Smaller carbon particles

306:犧牲基體 306: Sacrifice Matrix

A:豎直高度方向 A: Vertical height direction

Claims (77)

一種鋰(Li)離子電池，其包含： 一陽極； 與該陽極相對定位之一陰極； 定位於該陽極與該陰極之間之一多孔隔板；以及 與該陽極及該陰極接觸之一液體電解質，該陽極包含： 一導電基體；以及 沈積於該導電基體上之一第一膜，該第一膜包含一第一濃度之碳粒子，該等碳粒子係彼此接觸且經組配以界定該第一膜之一第一導電性，該等碳粒子中之各者包含由少層石墨烯片形成之多個聚集體，該多個聚集體形成經組配以經歷一鋰化之一多孔結構。A lithium (Li) ion battery comprising: An anode A cathode positioned opposite to the anode; A porous separator positioned between the anode and the cathode; and A liquid electrolyte in contact with the anode and the cathode, the anode includes: A conductive substrate; and A first film deposited on the conductive substrate, the first film including a first concentration of carbon particles, the carbon particles are in contact with each other and are configured to define a first conductivity of the first film, the Each of the carbon particles includes a plurality of aggregates formed of few-layer graphene sheets, and the plurality of aggregates form a porous structure that is configured to undergo a lithiation. 如請求項1之Li離子電池，其中該鋰化包括一間夾操作或一鍍覆操作中之任一者或多者。Such as the Li-ion battery of claim 1, wherein the lithiation includes any one or more of a clamping operation or a plating operation. 如請求項1之Li離子電池，其中該陽極及該陰極中之各者包含一電活性材料。The Li-ion battery of claim 1, wherein each of the anode and the cathode includes an electroactive material. 如請求項1之Li離子電池，其中該多孔結構經組配以在該等少層石墨烯片之接觸點之間提供電傳導。The Li-ion battery of claim 1, wherein the porous structure is configured to provide electrical conduction between the contact points of the few-layer graphene sheets. 如請求項1之Li離子電池，其中該多孔結構經組配以含有一熔融Li金屬。The Li ion battery of claim 1, wherein the porous structure is configured to contain a molten Li metal. 如請求項1之Li離子電池，其中該多孔結構經組配以接納該液體電解質。The Li ion battery of claim 1, wherein the porous structure is configured to receive the liquid electrolyte. 如請求項1之Li離子電池，其中該液體電解質經組配以促進多個Li離子在該多孔結構內之運輸。The Li ion battery of claim 1, wherein the liquid electrolyte is configured to promote the transportation of a plurality of Li ions in the porous structure. 如請求項1之Li離子電池，其進一步包含沈積於該第一膜上之一第二膜，其中該第二膜包含一第二濃度之以碳為主之粒子。The Li-ion battery of claim 1, further comprising a second film deposited on the first film, wherein the second film includes a second concentration of carbon-based particles. 如請求項8之Li離子電池，其中該第二濃度之以碳為主之粒子經組配以提供低於該第一導電性之該第二膜之一第二導電性。The Li ion battery of claim 8, wherein the second concentration of carbon-based particles are assembled to provide a second conductivity of the second film lower than the first conductivity. 如請求項3之Li離子電池，其中該電活性材料駐存於該陽極及該陰極中之一者或二者之孔隙中。The Li-ion battery of claim 3, wherein the electroactive material resides in the pores of one or both of the anode and the cathode. 如請求項3之Li離子電池，其中該電活性材料之比表面積(SSA)介於約1,635 m² /g與2,675 m² /g之間。Such as the Li-ion battery of claim 3, wherein the specific surface area (SSA) of the electroactive material is between about 1,635 m ² /g and 2,675 m ² /g. 如請求項3之Li離子電池，其中該電活性材料包含以下中之任一者或多者：預鋰化少層石墨烯(FLG)片、初始石墨烯、氧化石墨烯、還原氧化石墨烯、氟化石墨烯、氯化石墨烯、溴化石墨烯、碘化石墨烯、氫化石墨烯、氮化石墨烯、硼摻雜石墨烯、氮摻雜石墨烯、化學官能化石墨烯、其物理或化學活化或蝕刻型式、硫摻雜石墨烯，或其導電聚合物塗佈或接枝型式。Such as the Li-ion battery of claim 3, wherein the electroactive material comprises any one or more of the following: pre-lithiated few-layer graphene (FLG) sheets, initial graphene, graphene oxide, reduced graphene oxide, Fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, its physical or Chemically activated or etched type, sulfur-doped graphene, or its conductive polymer coated or grafted type. 如請求項1之Li離子電池，其中該多孔結構係由不依賴於一黏合劑之該等聚集體界定。Such as the Li-ion battery of claim 1, wherein the porous structure is defined by the aggregates that do not rely on a binder. 如請求項1之Li離子電池，其中該多孔結構經組配以成型為一實質上球形形狀。The Li-ion battery of claim 1, wherein the porous structure is assembled and formed into a substantially spherical shape. 如請求項14之Li離子電池，其中呈該實質上球形形狀之該多孔結構之尺寸為介於1-30 μm範圍內、＜ 50 μm或高於500 nm中之任一者或多者。The Li-ion battery of claim 14, wherein the size of the porous structure in the substantially spherical shape is any one or more of the range of 1-30 μm, <50 μm, or higher than 500 nm. 如請求項1之Li離子電池，其中該多孔結構包含經組配以併有矽(Si)之一活性Li間夾結構，該活性Li間夾結構之比容量介於約730 - 3,600 mAh/g之間。The Li-ion battery of claim 1, wherein the porous structure comprises an active Li intercalation structure combined with silicon (Si), and the specific capacity of the active Li intercalation structure is between about 730-3,600 mAh/g between. 如請求項12之Li離子電池，其中該化學官能化石墨烯包括選自以下之一官能基：醌、氫醌、四級銨化芳胺、硫醇、二硫化物、磺酸鹽(- SO₃ )、過渡金屬氧化物、過渡金屬硫化物或其一組合，以上物質包括經組配以與以下中之任一者或多者反應或併有以下中之任一者或多者之官能基：鎂(Mg)、鈣(Ca)、鋁(Al)、鍶(Sn)以及鋅(Zn)。Such as the Li ion battery of claim 12, wherein the chemically functionalized graphene includes a functional group selected from the group consisting of quinone, hydroquinone, quaternary ammonium arylamine, thiol, disulfide, sulfonate (-SO ₃ ), transition metal oxide, transition metal sulfide, or a combination thereof, the above substances include functional groups that are formulated to react with any one or more of the following or incorporate any one or more of the following : Magnesium (Mg), Calcium (Ca), Aluminum (Al), Strontium (Sn) and Zinc (Zn). 如請求項1之Li離子電池，其中該導電基體為一集電器。Such as the Li-ion battery of claim 1, wherein the conductive substrate is a current collector. 如請求項18之Li離子電池，其中該集電器至少部分以發泡體為主或衍生於發泡體且選自以下中之任一者或多者：一金屬發泡體、一金屬網、一金屬篩網、一穿孔金屬、一以片材為主之3D結構、一金屬纖維墊、一金屬奈米線墊、一導電聚合物奈米纖維墊、一導電聚合物發泡體、一導電聚合物塗佈的纖維發泡體、碳發泡體、石墨發泡體、碳氣凝膠、碳乾凝膠、石墨烯發泡體、氧化石墨烯發泡體、還原氧化石墨烯發泡體、碳纖維發泡體、石墨纖維發泡體以及剝離型石墨發泡體。The Li-ion battery of claim 18, wherein the current collector is at least partially foam-based or derived from foam and is selected from any one or more of the following: a metal foam, a metal mesh, A metal mesh, a perforated metal, a sheet-based 3D structure, a metal fiber mat, a metal nanowire mat, a conductive polymer nanofiber mat, a conductive polymer foam, and a conductive Polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam , Carbon fiber foam, graphite fiber foam and exfoliated graphite foam. 如請求項18之Li離子電池，其中該集電器成型為一箔。Such as the Li-ion battery of claim 18, wherein the current collector is formed into a foil. 如請求項3之Li離子電池，其中該電活性材料包含以下中之一或多者：一無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片。The Li-ion battery of claim 3, wherein the electroactive material comprises one or more of the following: a nanoparticle, a nanodisk, a nanosheet, a nanocoat or a nanosheet of an inorganic material. 如請求項21之Li離子電池，其中該等無機材料之奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片選自硒化鉍或碲化鉍、過渡金屬二硫屬化物或三硫屬化物、一過渡金屬硫化物、硒化物或碲化物、氮化硼或其一組合，其中該等奈米粒子、奈米盤、奈米薄片、奈米塗料或奈米片之厚度小於100 nm。Such as the Li-ion battery of claim 21, wherein the inorganic materials of nano particles, nano disks, nano flakes, nano coatings or nano flakes are selected from bismuth selenide or bismuth telluride, transition metal dichalcogenides Or trichalcogenide, a transition metal sulfide, selenide or telluride, boron nitride, or a combination thereof, where the thickness of the nanoparticle, nanodisk, nanosheet, nanocoat or nanosheet Less than 100 nm. 一種電化電池電極，其包含： 沈積於一導電基體上之一膜層，該膜層包含： 由正交熔合在一起之多個少層石墨烯片形成之一濃度之碳聚集體；以及 一多孔結構，該多孔結構係由該多個少層石墨烯片界定且經組配以在該多個少層石墨烯片中之任二個或更多個之間的接觸點之間提供電傳導或容納一電活性材料。An electrode for an electrochemical battery, which comprises: A film layer deposited on a conductive substrate, the film layer comprising: A single-concentration carbon aggregate is formed by a plurality of few graphene sheets fused together orthogonally; and A porous structure defined by the plurality of few-layer graphene sheets and configured to provide contact points between any two or more of the plurality of few-layer graphene sheets Electrically conduct or contain an electroactive material. 如請求項23之電化電池電極，其中該多個少層石墨烯片之一或多對鄰接石墨烯片包括藉由3 Å至20 Å之D-間距間隔開之一第一石墨烯片及一第二石墨烯片。For example, the electrochemical battery electrode of claim 23, wherein one or more pairs of adjacent graphene sheets of the plurality of few-layer graphene sheets include a first graphene sheet and a first graphene sheet separated by a D-spacing of 3 Å to 20 Å The second graphene sheet. 如請求項24之電化電池電極，其進一步包含一陽極，其中該電活性材料包含散佈於該陽極中之該D-間距中之一元素鋰(Li)。The electrochemical battery electrode of claim 24, further comprising an anode, wherein the electroactive material comprises lithium (Li), an element in the D-spacing dispersed in the anode. 如請求項25之電化電池電極，其進一步包含由該元素Li提供之多個Li離子。Such as the electrochemical battery electrode of claim 25, which further comprises a plurality of Li ions provided by the element Li. 如請求項23之電化電池電極，其進一步包含沈積於該膜上之一額外膜，其中該膜經組配以提供一第一導電性且該額外膜經組配以提供不同於該第一導電性之一第二導電性。The electrode of the electrochemical cell of claim 23, further comprising an additional film deposited on the film, wherein the film is configured to provide a first conductivity and the additional film is configured to provide a conductivity different from the first conductivity One of the second conductivity. 如請求項27之電化電池電極，該多孔結構包含： 經組配以被一液相電解質浸潤之多個互連通道，其中該第一導電性及該第二導電性均與該液相電解質中由該電活性材料提供之多個Li離子之一遷移成正比，其中該遷移係朝向與該電化電池電極實質上相對定位之一額外電化電池電極。Such as the electrode of the electrochemical battery of claim 27, the porous structure includes: It is assembled with a plurality of interconnecting channels infiltrated by a liquid electrolyte, wherein the first conductivity and the second conductivity both migrate with one of the Li ions provided by the electroactive material in the liquid electrolyte In direct proportion, the migration is directed to an additional electrochemical cell electrode positioned substantially opposite to the electrochemical cell electrode. 如請求項28之電化電池電極，其中該多個互連通道經組配以防止該電化電池電極或該額外電化電池電極中之任一者或多者上之Li離子積聚。The electrochemical cell electrode of claim 28, wherein the plurality of interconnecting channels are configured to prevent the accumulation of Li ions on any one or more of the electrochemical cell electrode or the additional electrochemical cell electrode. 如請求項23之電化電池電極，其中該多孔結構包含中尺度建構或微米尺度碎形建構中之任一者或多者。The electrochemical battery electrode of claim 23, wherein the porous structure includes any one or more of a mesoscale structure or a microscale fractal structure. 如請求項23之電化電池電極，其中該電活性材料包含一熔融Li金屬。The electrode of the electrochemical battery of claim 23, wherein the electroactive material comprises a molten Li metal. 如請求項31之電化電池電極，其中該熔融Li金屬經組配以被灌注至該多孔結構中。The electrode of the electrochemical battery of claim 31, wherein the molten Li metal is assembled to be poured into the porous structure. 如請求項23之電化電池電極，其中該多孔結構經組配以被一電解質浸潤。The electrode of the electrochemical battery of claim 23, wherein the porous structure is assembled to be infiltrated by an electrolyte. 如請求項33之電化電池電極，其中該電解質經組配以運輸Li離子。The electrode of the electrochemical battery of claim 33, wherein the electrolyte is assembled to transport Li ions. 如請求項33之電化電池電極，其中該多孔結構經組配以被於一液相或一凝膠相中之任一者或多者中之該電解質浸潤。The electrochemical battery electrode of claim 33, wherein the porous structure is configured to be infiltrated by the electrolyte in any one or more of a liquid phase or a gel phase. 如請求項33之電化電池電極，其中該電解質處於一聚合物相或一實質上固體電解質中間相中之任一者或多者中。The electrode of the electrochemical battery of claim 33, wherein the electrolyte is in any one or more of a polymer phase or a substantially solid electrolyte intermediate phase. 如請求項36之電化電池電極，其中該實質上固體電解質中間相包含一固態電解質。The electrode of the electrochemical battery of claim 36, wherein the substantially solid electrolyte intermediate phase comprises a solid electrolyte. 如請求項37之電化電池電極，其中該固態電解質經組配以至少實質上防止或減少Li樹枝狀結晶之形成、短路之形成或該固態電解質之滲漏中的任一者或多者。The electrochemical battery electrode of claim 37, wherein the solid electrolyte is configured to at least substantially prevent or reduce any one or more of the formation of Li dendrites, the formation of short circuits, or the leakage of the solid electrolyte. 如請求項37之電化電池電極，其中該固態電解質選自一固體聚合物電解質、一凝膠聚合物電解質或一非聚合物電解質中之任一者或多者。The electrode of an electrochemical battery according to claim 37, wherein the solid electrolyte is selected from any one or more of a solid polymer electrolyte, a gel polymer electrolyte, and a non-polymer electrolyte. 如請求項37之電化電池電極，其中該固態電解質進一步包含溶解於一聚合物主體中之一Li鹽。The electrode of the electrochemical battery of claim 37, wherein the solid electrolyte further comprises a Li salt dissolved in a polymer body. 如請求項40之電化電池電極，其中該聚合物主體包括以下中之任一者或多者：聚乙二醇(PEO)、聚偏二氟乙烯(polyvinylidene fluoride/polyvinylidene difluoride，PVDF)、聚(對苯醚) (PPO)或聚、聚(偏二氟乙烯-共-六氟丙烯) (PVDF-HFP)、聚(甲基丙烯酸甲酯) (PMMA)、聚苯乙烯磺酸酯(PSS)以及此等聚合物之鹽(Li或Na鹽)、PAN、PANI。For example, the electrode of the electrochemical battery of claim 40, wherein the polymer body includes any one or more of the following: polyethylene glycol (PEO), polyvinylidene fluoride/polyvinylidene difluoride (PVDF), poly( P-phenylene ether) (PPO) or poly, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(methyl methacrylate) (PMMA), polystyrene sulfonate (PSS) And the salts of these polymers (Li or Na salts), PAN, PANI. 如請求項36之電化電池電極，其中該實質上固體電解質中間相包含於一聚合物基質中捕獲之一液體組分或一非聚合物固體電解質中之一者或另一者。The electrochemical battery electrode of claim 36, wherein the substantially solid electrolyte intermediate phase contains one or the other of a liquid component trapped in a polymer matrix or a non-polymer solid electrolyte. 如請求項42之電化電池電極，其中該液體組分經組配以促進Li離子運輸。Such as the electrochemical battery electrode of claim 42, wherein the liquid component is formulated to promote Li ion transport. 如請求項42之電化電池電極，其中該非聚合物固體電解質包含一實質上陶瓷材料。The electrode of the electrochemical battery of claim 42, wherein the non-polymer solid electrolyte comprises a substantially ceramic material. 如請求項42之電化電池電極，其中該非聚合物固體電解質包含以下中之任一者或多者：Li超離子導體(LISICON)、包括一石榴石型Li₇ La₃ Zr₂ O₁₂ (LLZO)之一併有陶瓷奈米纖維之複合材料、包括鈣鈦礦由鈦酸鈣構成之氧化鈣鈦礦物。The electrode of the electrochemical battery of claim 42, wherein the non-polymer solid electrolyte comprises any one or more of the following: Li super ionic conductor (LISICON), including a garnet type Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) One of them is a composite material of ceramic nanofibers, including perovskite oxide perovskite mineral composed of calcium titanate. 如請求項42之電化電池電極，其中該非聚合物固體電解質之厚度介於約0.5 μm至40 μm之範圍內。The electrochemical battery electrode of claim 42, wherein the thickness of the non-polymer solid electrolyte is in the range of about 0.5 μm to 40 μm. 如請求項46之電化電池電極，其中該厚度經組配以實質上防止Li樹枝狀結晶形成或生長中之任一者或多者。The electrochemical battery electrode of claim 46, wherein the thickness is configured to substantially prevent any one or more of the formation or growth of Li dendrites. 如請求項23之電化電池電極，其中該多孔結構中之一通道進一步包含： 經組配以提供一Li離子管道之一第一部分； 經組配以促進快速Li離子運輸之一第二部分；以及 經組配以限制該電活性材料之一第三部分。Such as the electrochemical battery electrode of claim 23, wherein one of the channels in the porous structure further comprises: It is assembled to provide the first part of a Li ion pipeline; The second part is configured to promote rapid Li ion transport; and It is configured to limit a third part of the electroactive material. 如請求項23之電化電池電極，其中導電性介於約1,000 S/m與約20,000 S/m之間之範圍內。The electrode of the electrochemical battery of claim 23, wherein the conductivity is within a range between about 1,000 S/m and about 20,000 S/m. 如請求項23之電化電池電極，其進一步包含： 沈積於該膜層上之一或多個額外膜層，該一或多個額外膜層中之任一個或多個經組配以提供一導電性，該導電性係相對於一緊接在前之膜層而言在與該導電基體實質上正交之一方向成比例地降低。Such as the electrode of the electrochemical battery of claim 23, which further includes: One or more additional film layers are deposited on the film layer, and any one or more of the one or more additional film layers are configured to provide a conductivity that is relative to an immediately preceding one The film layer is reduced in proportion to a direction substantially orthogonal to the conductive substrate. 如請求項23之電化電池電極，其中一固體-電解質界面(SEI)形成於該多孔結構之一鄰近區域內。Such as the electrode of the electrochemical cell of claim 23, wherein a solid-electrolyte interface (SEI) is formed in an adjacent area of the porous structure. 如請求項51之電化電池電極，其中該電化電池進一步包含定位於該多孔結構之一鄰近區域內之一人工固體-電解質界面(ASEI)。The electrode of the electrochemical cell of claim 51, wherein the electrochemical cell further comprises an artificial solid-electrolyte interface (ASEI) positioned in a vicinity of the porous structure. 如請求項52之電化電池電極，其中該ASEI在該多孔結構形成期間原位形成或異地形成為一塗層、一膜或一反應物中之任一者或多者。The electrochemical battery electrode of claim 52, wherein the ASEI is formed in situ or heterogeneously formed as any one or more of a coating, a film, or a reactant during the formation of the porous structure. 如請求項23之電化電池電極，其中該多孔結構包括一或多個親鋰官能化表面。The electrochemical battery electrode of claim 23, wherein the porous structure includes one or more lithium-philic functionalized surfaces. 如請求項54之電化電池電極，其中該一或多個親鋰官能化表面經組配以提供Li吸附中心。The electrochemical battery electrode of claim 54, wherein the one or more lithium-philic functionalized surfaces are configured to provide Li adsorption centers. 一種製造一陽極之方法，該方法包含： 以一第一濃度位準成核多個碳粒子； 基於該第一濃度位準在一犧牲基體上形成一第一膜，該等碳粒子中之各者係利用由熔合在一起之少層石墨烯(FLG)片形成之多個聚集體界定； 基於該等FLG片界定一多孔結構；以及 將一熔融鋰(Li)金屬灌注至該多孔結構中。A method of manufacturing an anode, the method comprising: Nucleate a plurality of carbon particles at a first concentration level; A first film is formed on a sacrificial substrate based on the first concentration level, and each of the carbon particles is defined by a plurality of aggregates formed by fused few-layer graphene (FLG) sheets; Define a porous structure based on the FLG sheets; and A molten lithium (Li) metal is poured into the porous structure. 如請求項56之方法，其進一步包含基於該多個碳粒子界定多個互連多孔通道。The method of claim 56, further comprising defining a plurality of interconnected porous channels based on the plurality of carbon particles. 如請求項56之方法，其進一步包含藉由在該第一膜上以一第二濃度位準成核該等碳粒子來形成一第二膜。The method of claim 56, further comprising forming a second film by nucleating the carbon particles at a second concentration level on the first film. 如請求項58之方法，其中該第一膜經組配以提供一第一導電性且該第二膜經組配以提供不同於該第一導電性之一第二導電性。The method of claim 58, wherein the first film is configured to provide a first conductivity and the second film is configured to provide a second conductivity different from the first conductivity. 如請求項59之方法，其中第二導電性低於該第一導電性。The method of claim 59, wherein the second conductivity is lower than the first conductivity. 如請求項56之方法，其中該第一膜之平均厚度介於約10 µm與約200 µm之間之範圍內。The method of claim 56, wherein the average thickness of the first film is in a range between about 10 µm and about 200 µm. 如請求項56之方法，其進一步包含在一卷軸式處理設備上生長碳粒子。Such as the method of claim 56, which further comprises growing carbon particles on a reel type processing device. 如請求項56之方法，其進一步包含： 將該熔融Li金屬氣化至一金屬箔上；以及 將該熔融Li金屬自該金屬箔捲至該多孔結構中。Such as the method of claim 56, which further includes: Vaporizing the molten Li metal onto a metal foil; and The molten Li metal is rolled from the metal foil into the porous structure. 如請求項56之方法，其進一步包含製備該陽極以與藉由化學官能化或硫化中之任一者或多者製備之一陰極一起參與Li離子之一可逆遷移。The method of claim 56, further comprising preparing the anode to participate in a reversible migration of Li ions together with preparing a cathode by any one or more of chemical functionalization or sulfurization. 如請求項57之方法，其進一步包含在該多孔結構上使多個石墨烯薄片緻密。The method of claim 57, further comprising densifying a plurality of graphene flakes on the porous structure. 一種用於產生一鋰(Li)離子電池陽極之方法，該方法進一步包含： 在一基體上沈積第一多個碳粒子； 形成一第一膜，該第一膜係經組配以基於該第一多個碳粒子提供一第一導電性，該第一多個碳粒子中之各碳粒子包含： 多個3D聚集體，該多個3D聚集體係由正交熔合在一起之少層石墨烯(FLG)片形成且經組配以界定一多孔結構；以及 形成於該多孔結構中之一多孔配置；以及 將一熔融Li金屬灌注至該多孔結構中。A method for producing a lithium (Li) ion battery anode, the method further comprising: Depositing a first plurality of carbon particles on a substrate; A first film is formed, the first film is configured to provide a first conductivity based on the first plurality of carbon particles, and each of the first plurality of carbon particles includes: A plurality of 3D aggregates, the plurality of 3D aggregate systems are formed by orthogonally fused together few-layer graphene (FLG) sheets and assembled to define a porous structure; and A porous configuration formed in the porous structure; and A molten Li metal is poured into the porous structure. 如請求項66之方法，其進一步包含： 在該第一膜上沈積第二多個碳粒子；以及 形成一第二膜，該第二膜係經組配以基於該第二多個碳粒子提供一第一導電性。Such as the method of claim 66, which further includes: Depositing a second plurality of carbon particles on the first film; and A second film is formed, and the second film is configured to provide a first conductivity based on the second plurality of carbon particles. 如請求項66之方法，其進一步包含基於該熔融Li金屬之一黏性阻力選擇該熔融Li金屬之一灌注速率。The method of claim 66, further comprising selecting a pouring rate of the molten Li metal based on a viscous resistance of the molten Li metal. 如請求項66之方法，其中該熔融Li金屬經組配以與該第一多個碳粒子中之任一個或多個反應來產生碳化物。The method of claim 66, wherein the molten Li metal is configured to react with any one or more of the first plurality of carbon particles to produce carbides. 如請求項66之方法，其進一步包含： 將於一氣相中之該熔融Li金屬浸潤至該多孔結構中； 在由該熔融Li金屬提供之任一個或多個Li離子與該多孔結構之一或多個暴露表面之間引發一化學反應；以及 由該一或多個暴露表面形成一或多個親鋰表面。Such as the method of claim 66, which further includes: Infiltrating the molten Li metal in a gas phase into the porous structure; Initiating a chemical reaction between any one or more Li ions provided by the molten Li metal and one or more exposed surfaces of the porous structure; and One or more lithium-philic surfaces are formed from the one or more exposed surfaces. 如請求項70之方法，其進一步包含用包括鹵素或金屬氧化物中之任一者或多者之活性元素塗佈該等親鋰表面中之任一個或多個。The method of claim 70, further comprising coating any one or more of the lithium-philic surfaces with an active element including any one or more of halogen or metal oxide. 如請求項71之方法，其進一步包含： 用具有一低於Li之表面能之任一個或多個元素塗佈該等親鋰表面中之任一個或多個；以及 用具有一低於Li之表面能之任一個或多個元素促進該等親鋰表面中之任一個或多個之一Li潤濕增強。Such as the method of claim 71, which further includes: Coating any one or more of the lithium-philic surfaces with any one or more elements having a surface energy lower than Li; and Any one or more elements having a surface energy lower than Li are used to promote the wetting enhancement of Li on any one or more of the lithium-philic surfaces. 如請求項66之方法，其進一步包含： 藉由將一金屬粉末或包括碳化矽(SiC)之一含金屬化合物中之任一者或多者併入一碳預形成物中來產生一黏合劑。Such as the method of claim 66, which further includes: A binder is produced by incorporating any one or more of a metal powder or a metal-containing compound including silicon carbide (SiC) into a carbon preform. 如請求項66之方法，其中Li潤濕包含對一界面表面張力進行工程改造。Such as the method of claim 66, wherein Li wetting includes engineering an interfacial surface tension. 如請求項66之方法，其中Li潤濕包含一Li界面及該多孔結構之一暴露表面處之一或多個化學反應。The method of claim 66, wherein Li wetting includes one or more chemical reactions at a Li interface and an exposed surface of the porous structure. 如請求項72之方法，其中該Li潤濕增強包含： 在界面處添加一定量之摻雜劑；以及 影響對應於該量摻雜劑之該Li潤濕之一程度。Such as the method of claim 72, wherein the Li wetting enhancement comprises: Add a certain amount of dopant at the interface; and The influence corresponds to a degree of the Li wetting of the amount of dopant. 如請求項66之方法，其進一步包含： 在該多孔結構之一或多個暴露表面中之任一個處控制羥基(hydroxy/hydroxyl，OH)吸附。Such as the method of claim 66, which further includes: The hydroxy/hydroxyl (OH) adsorption is controlled at any one of one or more exposed surfaces of the porous structure.

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