200835026 九、發明說明： 【發明所屬技術領域】 本發明係關於鋰離子電化學電池包括電容器、超電容 器及電池組之組成之改良。 5 【先前技術】200835026 IX. DESCRIPTION OF THE INVENTION: Field of the Invention The present invention relates to improvements in the composition of lithium ion electrochemical cells including capacitors, ultracapacitors, and battery packs. 5 [Prior technology]
本發明所使用之中孔材料偶爾稱作為「夺米孔隙。作 因前置詞「奈米」嚴格表示，，而此種材料^孔隙可」能= 10 8米至10 9之範圍’故較佳於此處稱作為「中孔。 雖然嚴格言之，「電池組」-詞表示兩個或多個電池的 10配置’但於此處其常用定義表示一種儲存及釋放電能之裳 置’而與其包含一個電池或數個電池無關。 電子業界有朝向「收斂」的趨勢，亦即諸如行動電爷 及個人數位助理器CPDA)等裝置之功能增加’已經增加:電 池組的能量及電力的需求。目前，發明人發現容量（能量） 15改良的最大範圍係在於負電極的發展。大部分商業鋰離 電池目前係使用基於碳之負電極。碳之電荷儲存容量典型 係於300亳安培小時/克（mAh/g)之範圍。 20 碳之替代品為可於鋰於低電位形成合金之材料，諸如 锡、矽及鋁。此等材料具有高達2000 mAh/g之電荷儲存六 量。但鋰***此等材料中伴隨有結構的顯著膨脹。如此= 成材料的快速機械崩潰，電池效能表現為電池週期I命= 佳。此外，充電期間電極材料的膨脹，造成整 除 M兔池組的 )騰，結果導致其它效能考量及安全性考量。如此，此等 内夺量材料的商業化至今為止受限制，碳電極仍然佔有主 5 200835026 要技術。 於化學通訊’ 1999,4,331-332，J.R· 〇wen揭示使用液晶 樣板迷徑製造之電沉積錫膜所組成之鋰離子電池負電極。 報告陳述··「預期廣泛中孔度將顯著降低於膨脹期間之内部 5應力，如此減少電極之機械降級」。但發現週期壽命差。 • 發明人今日出乎意外地發現若液晶樣板化材料係呈由 液晶相藉電化學沉積所形成之粉末形式，而非電沉積薄膜 馨料，則·壽命可改良超過先前揭示之職壽命。雖然 發明人不欲受任何理論所限，但相信由於基於顆粒之電極 1〇特有之顆粒間的孔隙度，加上由液晶樣板所提供各個顆粒 内部之中孔度，粉末形式具有吸收材料晶格膨脹超過由樣 板化中孔度所提供之雜之改良能力。結果，發明人發現 液晶樣板化材料之粉末形式提供週期循環期間具有優^之 抗容量衰減抗性，如此提供遠更為改良之週期壽命之能力。 15 【發^明内溶1】 譽#此本發明係關於一種電化學電池，包含一正電極、 7貞電極及1水性電解質，其特徵在於該負電極包含可 形成與-撐體接觸之链***合金之中孔材料粉末，該粉末 係由液晶相化學沉積。 20【實施方式】 液曰曰相之製備及使用係揭示於美國專利案6,503,382及 6,2〇3,925，其揭*係則丨財式併入此處。 本發明之電化學電池為電容器、超電容器或電池组。 當為電池組時，通常為二次電池組，亦即可重複充電式電 6 200835026 池組。 可形成鋰***合金之材料町為一種元素（金屬或類金 屬）；或可為一種或多種可形成鋰***合金之元素與一種或 多種無法形成此種***合金之元素之混合物或合金；兩種 5或多種可形成鋰***合金之元素之混合物或合金。具有鋰 ***活性之元素之實例為鋁、矽、鎂、錫、鉍、鉛、及銻。 鋼對鋰***為純性，但銅與活性元素諸如錫之合金可能為 活性。其它鈍性元素包括鎳、鈷及鐵。有一優點為包括此 等鈍性合金化元素，其存在可有效稀釋活性材料，因此於 週期循環時之膨脹減少，結果導致進一步改良之週期壽 巧。較佳活性元素為鍚，最佳係用作為與鈍性元素之合金， 最佳為用作為與銅之合金。 典型負電極包含活性層沉積於適當基材上或基材内。 15 '舌眭層可由活性電極粉末所組成，較佳活性電極粉末加聚 ΰ物黏結劑，其將顆粒黏結在一起，以及視需要可包括傳 &性提升添加劑諸如碳。雖然較佳活性層須含有傳導性提 升添加劑，但若有所需可刪除。 活性層須接觸基材且較佳於基材上，基材最佳為金屬 20羯諸如銅猪。但也可使用多孔基材諸如泡洙體。可使用標 準電解質及正電極。 用於本餐明之具有叙***活性之中孔材料之孔隙度可 ;寬廣ι&圍改欠，例如由13%至8Ό%。但較佳材料孔隙度係 由38%至8〇%。此處孔隙度係由氮孔隙計量術(β印測量值 外出大致上餐現週期壽命隨著孔隙度的增加而改良。 7 200835026 但孔隙度過高，將導致活性材料量的減少，因而造成電池 效能的降低。較佳孔隙度係於由42%至75%之範圍，更佳由 44%至70%之範圍。最佳孔隙度係由5〇%至65%之範圍。 具有鋰***之活性材料其本身不可能有足夠機械強度 5來用作為電極，如此較佳係用於一撐體上之電化學電池 中，撐體也可用作為集電器。如此撐體材料較佳為電傳導 性，較佳有足夠機械強度來當形成儘可能較薄之薄膜時保 • 持完好。用作為撐體之適當材料包括銅、鎳及鈷，其中對 成本及導電性二者而言以鋼為較佳。 1〇 & 了提升電極的導電性，多孔材料較佳係混合導電性 粉末，例如：碳較佳係呈石墨、非晶形碳、或乙快黑形式·， 錄；或録。若有所需，也可與黏結劑混合，黏結劑諸如乙 烯丙烯二烯單體(EPDM)、苯乙烯丁二稀橡膠(SBR)、絲 甲基纖維素(CMC)、聚乙烯基氣化二婦(pVDF)、聚四氣乙 15烯(PTFE)、聚乙酸乙稀g旨或其中任二者或多者之混合物。 • ^孔材料、導電粉末、及任選地，黏結劑可與有機溶劑混 合，有機溶劑諸如為己烷、水、環己烷、庚烷 '己烷、或 N甲基比各％酮’所得糊料施用至撐體，隨後藉蒸發去除 有機〜卜留下多孔材料與導電粉末以及視需要所使用之 20 黏結劑之渴*合物。 电化學電池也含有正電極。正電極可為任 鋰離子電池作兔·p+k , 乍為正讀之種材料。此等材料之實例包 極，二H1Mn〇2、LiNic。02、或随疏。〇2。類似負電 續佳為於撐體上之18、銅、錫或金且較佳為鋁。 8 200835026 5 10 15 鲁 20 電極同樣可為任一 硼酸鋰、全氯酸鋰。 〇材料，例如六氟磷酸鋰、四 伸乙酸、碳酸二伸乙酸鋰於適當溶劑，例如破酸 中任:種或多種之混二:酸二甲嘴、碳酸伸丙醋、或其 膜、多例如微孔聚丙婦膜或聚乙烯 用於本發明中作c與聚乙浠之組合。 種已知之化悤 〜、、、電極之中孔材料之製備可為任一 中孔材料由2=?。例如形成液晶混合物，造成 積，包缸貝夕種化學方法可用來執行此項沉所使用沉積。當然咖 舉^積方法將依據魏積之材料之本質決定。 —個材料:之種製備中孔材料之方法包含由包含至少 料至—源有機導向劑及溶劑之混合物中，沉積該材 材料之孔撐體上，故由該來源材料與可製造期望之中孔 體上σ物反應，直至足量材料已經沉積來於該多孔撐 體上2中孔層’以及然後移除有機導向劑來於該多孔撐 構係^—中孔層’該中孔層較佳具有實質規則之孔隙結 種松粗例如由25奈米至50奈米之期望範圍之均勻孔徑。此 料隨後可使用諸如球磨等技術來加卫成為粉末形式。 用於混合物之來源材料之本質將依據欲製造之材料本 :屬：。至於另一替代之道，形成中孔材料之該材料可為 屬或其它可耩逖原反應或其它化學反應而可沉積之材 料。於此種情況下，混合物包含金屬或其它元素之來源材 料溶解於_，及足4錢結構導向财提供向液性液晶 9 200835026 相。 適當來源材料之實例包括可還原成為該元素之元素化 0物舉例δ之，右期望之材料為錫，則應使用錫化合物， 例如甲磺酸錫、SnBF4、SnCH3S〇3、SnCl4、或SnCl2。若期 5望製造兩種或多種元素諸如活性元素與鈍性元素之混合 物則應使用個別元素化合物之混合物。鈍性元素之來源 貝例包括CuS〇4、CuCl2、CoCl2。溶劑本質並無特殊限制， 通常為水性。 種或夕種來源材料可呈混合物使用來還原成為一種 1〇或多種金屬或其它材料。如此經由適當選擇來源材料，可 如所需控制多孔材料之組成。適當材料包括前文就電沉積 方法所述之材料。 還原劑用來還原混合物。適當還原劑包括金屬（諸如 鋅、鐵、或鎂）、次磷酸氫鈉、二甲硼烷、氫氣、及肼，較 15佳為次鱗酸鈉或二甲刪烧。 較佳’混合物之pH可調整至2至12之範圍之數值。溫度 通常係維持於15。〇至i〇〇°c，較佳i8°c至80°C及更佳20°C至 60°C之範圍。 混合物及還原劑放置一段足夠時間來沉澱多孔材料， 20典型係於室溫放置隔夜。依據反應物之本質而定，混合物 可放置15分鐘至4週，典型放置約μ小時。於反應後，通常 期望處理多孔材料來移除於合成中所使用之材料，包括結 構導向劑、烴添加劑、未反應之來源材料及離子性雜質， 例如藉溶鮮取，或於氮巾分解以及於氧巾轉(假燒)來去 10 200835026 可能無需此項 除合、成中所使用之材料。但用於某些用途 處理。 5The mesoporous material used in the present invention is occasionally referred to as "the rice pore. The premise "nano" is strictly indicated, and the material can be in the range of 10 8 to 10 9". This is referred to herein as "middle hole. Although strictly speaking, the "battery pack" - word means the 10 configuration of two or more batteries 'but the common definition here means a kind of storage and release of electric energy' and contains it No battery or several batteries. The electronics industry has a tendency to "converge", that is, the increased functionality of devices such as mobile e-mail and personal digital assistant CPDA has increased: the energy and power requirements of the battery pack. At present, the inventors have found that the largest range of improvement in capacity (energy) 15 lies in the development of the negative electrode. Most commercial lithium ion batteries currently use carbon-based negative electrodes. The charge storage capacity of carbon is typically in the range of 300 ampere-hours per gram (mAh/g). 20 Carbon substitutes are materials that form alloys at low potentials such as tin, antimony and aluminum. These materials have a charge storage of up to 2000 mAh/g. However, the insertion of lithium into these materials is accompanied by a significant expansion of the structure. So = rapid mechanical breakdown of the material, battery performance is the battery cycle I life = good. In addition, the expansion of the electrode material during charging causes the entanglement of the M rabbit pool, resulting in other performance considerations and safety considerations. As such, the commercialization of such internal materials has been limited to date, and carbon electrodes still occupy the main technology. In Chemical Communications' 1999, 4, 331-332, J. R. 〇wen discloses a lithium ion battery negative electrode composed of an electrodeposited tin film manufactured by using a liquid crystal sample. Report Statement · "It is expected that the extensive mesoporosity will be significantly reduced by the internal 5 stress during expansion, thus reducing the mechanical degradation of the electrode." However, it was found that the cycle life was poor. • The inventors have unexpectedly discovered today that if the liquid crystal template material is in the form of a powder formed by electrochemical deposition of a liquid crystal phase, rather than an electrodeposited film, the lifetime can be improved beyond the previously disclosed life. Although the inventors do not wish to be bound by any theory, it is believed that due to the porosity between the particles of the particle-based electrode and the porosity of the interior of each particle provided by the liquid crystal template, the powder form has an absorbing material lattice. The expansion exceeds the improved ability provided by the porosity of the template. As a result, the inventors have discovered that the powder form of the liquid crystal tiling material provides excellent resistance to capacity decay during cycle cycling, thus providing a much more improved cycle life. 15 The invention relates to an electrochemical cell comprising a positive electrode, a 7-electrode electrode and an aqueous electrolyte, characterized in that the negative electrode comprises a chain which can form a contact with the support body. A pore material powder is inserted into the alloy, which is chemically deposited from the liquid crystal phase. [Embodiment] The preparation and use of liquid helium phase are disclosed in U.S. Patent Nos. 6,503,382 and 6,2,3,925, the disclosure of which is incorporated herein by reference. The electrochemical cell of the present invention is a capacitor, an ultracapacitor or a battery. When it is a battery pack, it is usually a secondary battery pack, and it can also be a rechargeable battery. The material from which the lithium intercalation alloy can be formed is an element (metal or metalloid); or may be a mixture or alloy of one or more elements capable of forming a lithium intercalation alloy and one or more elements which are incapable of forming such an intercalation alloy; 5 or more mixtures or alloys that form elements of the lithium intercalation alloy. Examples of the element having lithium insertion activity are aluminum, bismuth, magnesium, tin, antimony, lead, and antimony. Steel is pure for lithium insertion, but alloys of copper with active elements such as tin may be active. Other passive elements include nickel, cobalt and iron. One advantage is the inclusion of such passive alloying elements which are effective in diluting the active material so that the expansion during cycle cycling is reduced, resulting in a further improved cycle life. The preferred active element is ruthenium, which is preferably used as an alloy with a passive element, and is preferably used as an alloy with copper. A typical negative electrode comprises an active layer deposited on a suitable substrate or within a substrate. The 15' tongue layer may be composed of an active electrode powder, preferably a reactive electrode powder plus a cerium binder which bonds the granules together and, if desired, a passivating additive such as carbon. Although the preferred active layer must contain a conductivity enhancing additive, it can be removed if desired. The active layer must be in contact with the substrate and preferably on the substrate. The substrate is preferably a metal such as a copper pig. However, porous substrates such as blister bodies can also be used. Standard electrolytes and positive electrodes can be used. The porosity of the pore material used for the insertion of the active ingredient in the present invention can be broadened, for example, from 13% to 8Ό%. However, the preferred material porosity ranges from 38% to 8%. Here, the porosity is determined by nitrogen porosimetry (the β-printed value is generally improved. The life expectancy of the meal is improved with the increase of porosity. 7 200835026 However, if the porosity is too high, the amount of active material will decrease, thus causing the battery. The efficiency is reduced. The preferred porosity is in the range of 42% to 75%, more preferably in the range of 44% to 70%. The optimum porosity is in the range of 5〇% to 65%. The material itself may not have sufficient mechanical strength 5 to be used as an electrode, so it is preferably used in an electrochemical cell on a support, and the support can also be used as a current collector. Such a support material is preferably electrically conductive. Preferably, there is sufficient mechanical strength to maintain the film as thin as possible. Suitable materials for the support include copper, nickel and cobalt, of which steel is preferred for both cost and conductivity. 1〇& The conductivity of the lift electrode is preferred, and the porous material is preferably a mixed conductive powder. For example, carbon is preferably graphite, amorphous carbon, or B-black form, or recorded. Need, can also be mixed with the binder, bonding Such as ethylene propylene diene monomer (EPDM), styrene butyl rubber (SBR), silk methyl cellulose (CMC), polyvinyl vaporized two women (pVDF), polytetraethylene ethene (PTFE) Polyacetate or a mixture of two or more thereof. • The pore material, the conductive powder, and optionally the binder may be mixed with an organic solvent such as hexane, water or cyclohexane. The paste obtained from the alkane, heptane 'hexane, or N methyl group than the % ketone' is applied to the support, and then the organic material is removed by evaporation to leave the porous material and the conductive powder and the 20 binder used as needed. The electrochemical cell also contains a positive electrode. The positive electrode can be a lithium ion battery for rabbits, p+k, and 乍 is a material for reading. Examples of such materials are polar, two H1Mn〇2, LiNic. 02, or with sparse. 〇 2. Similar to negative electrons are preferably 18, copper, tin or gold on the support and preferably aluminum. 8 200835026 5 10 15 Lu 20 electrode can also be any lithium borate, perchlorine Lithium acid. 〇 materials, such as lithium hexafluorophosphate, tetraacetic acid, lithium carbonate, in a suitable solvent, such as acid-breaking Medium: a mixture of two or more kinds: acid dimethyl hydrazine, carbonic acid propylene vinegar, or a film thereof, such as microporous polypropylene film or polyethylene used in the present invention as a combination of c and polyethyl hydrazine. It is known that the preparation of the pore material in the electrode can be any of the mesoporous materials from 2 = ?. For example, the formation of a liquid crystal mixture, resulting in a product, the cylinder chemical method can be used to perform deposition of the sink. Of course, the method of caving will be determined according to the nature of the material of Wei. The material: the method for preparing the mesoporous material comprises the hole for depositing the material from the mixture containing at least the source of the organic guiding agent and the solvent. On the support, the source material is reacted with the sigma on the desired pores until a sufficient amount of material has been deposited on the porous support 2 mesoporous layer' and then the organic directing agent is removed Porous support system - mesoporous layer 'The mesoporous layer preferably has a substantially regular pore size, such as a uniform pore size of the desired range from 25 nm to 50 nm. This material can then be applied in powder form using techniques such as ball milling. The nature of the source material used in the mixture will depend on the material to be manufactured: As a further alternative, the material forming the mesoporous material can be a material that can be deposited by other genus or other chemical reaction or other chemical reaction. In this case, the mixture contains a source material of metal or other elements dissolved in _, and the structure of the foot is supplied to the liquid liquid crystal 9 200835026 phase. Examples of suitable source materials include elemental materials which can be reduced to this element are exemplified by δ, and the right desired material is tin, and tin compounds such as tin methanesulfonate, SnBF4, SnCH3S〇3, SnCl4, or SnCl2 should be used. If a mixture of two or more elements such as an active element and a passive element is to be produced, a mixture of individual elemental compounds should be used. Sources of passive elements Shell examples include CuS〇4, CuCl2, and CoCl2. The nature of the solvent is not particularly limited and is usually aqueous. The material of the species or the genus may be used in a mixture to reduce to one or more metals or other materials. Thus, by appropriately selecting the source material, the composition of the porous material can be controlled as desired. Suitable materials include those previously described for the electrodeposition process. A reducing agent is used to reduce the mixture. Suitable reducing agents include metals such as zinc, iron, or magnesium, sodium hydrogen hypophosphite, diborane, hydrogen, and helium, more preferably 15 or less. Preferably, the pH of the mixture can be adjusted to a value in the range of 2 to 12. The temperature is usually maintained at 15. 〇 to i 〇〇 °c, preferably in the range of i8 ° C to 80 ° C and more preferably 20 ° C to 60 ° C. The mixture and reducing agent are allowed to stand for a sufficient period of time to precipitate the porous material, 20 typically placed overnight at room temperature. Depending on the nature of the reactants, the mixture can be placed for 15 minutes to 4 weeks, typically for about μ hours. After the reaction, it is generally desirable to treat the porous material to remove materials used in the synthesis, including structure directing agents, hydrocarbon additives, unreacted source materials, and ionic impurities, such as by solvent extraction or by decomposition of the nitrogen blanket. In the oxygen towel turn (sham burn) to go 10 200835026 may not need the material used in this division, Chengzhong. However, it is used for certain purposes. 5
10 有機結構導向劑含括於混合物内來對混合物提供均晰 向液性液晶相。相信液晶相係作為中孔材料沉積 ： 導向介質或樣板。經由控制向液性液晶相之奈米結構7 孔材料可合成為具有相對應之奈米結構。舉例古之，t 準拓樸學六面射目娜权纽㈣將^㈣設置^ 面體晶m统’而由標準拓樸學立方體減形成之多^ 材料將具有孔隙《於立方齡樸學㈣之系統。同理，具 有層狀奈米結構之多孔材料可由層狀相沉積。如此，經由探 勘由液晶相所具有之豐富向液性多晶形，液晶技術允許精^ 控制多孔材料結構，允許具有長範圍空間週期性及方向週二 性之均勻孔徑孔隙分布之明破界定多孔材料之合成。10 The organic structure directing agent is included in the mixture to provide a liquid crystal phase to the mixture. It is believed that the liquid crystal phase is deposited as a mesoporous material: a guiding medium or a template. The nanoporous structure 7 pore material controlled by the liquid crystal phase can be synthesized to have a corresponding nanostructure. For example, the ancient one, t quasi topography, six-sided shot, Naquan New (four) will ^ (four) set ^ surface crystal m system ' and formed by the standard topology cubes ^ material will have pores in the cube age (four) system . Similarly, a porous material having a layered nanostructure can be deposited from a lamellar phase. Thus, by exploring the rich liquid-to-liquid polymorphism of the liquid crystal phase, the liquid crystal technology allows precise control of the porous material structure, allowing the porous material to be defined by a uniform pore size distribution with a long range of spatial periodicity and direction. Synthesis.
可幵/成均貝向液性液晶相之任何適當兩親性有機化合 15物可用作為結構導向劑，結構導向劑可為低莫耳量或為 合物。此等結構導向劑包括偶爾稱作為有機導向劑之化合 物。為了提供所需均質液晶相，以溶劑、來源材料及兩親 性化合物之總重為基準，兩親性化合物通常係使用高濃 度典型為至少約10%重量比，較佳至少為2〇%重量比，及 20更佳至少為30%重量比。 較佳，有機結構導向劑包含式RQ有機界面活性劑化合 物其中R表示含6至約60個碳原子且較佳由12至18個碳原 子之線性或分找基、絲1絲找絲基；以及Q 表不選自於下示之基團：[〇(CH2L]n〇H，其中爪為】至約4 11 200835026 之整數且較佳m為2,以及n為2至約60之整數且較佳為4至 12 ;氮係鍵結至選自於含至少4個碳原子之烷基、芳基、芳 烷基及烷基芳基中之至少一個基團；以及填及硫鍵結至至 少2個氧原子。其它適當結構導向劑包括單醣類、磷脂類、 5 及糖脂類。 其它適當化合物包括式R!R2Q之界面活性有機化合 物’其中1及112表示含6至約36個碳原子之芳基或烷基或其 組合；以及Q表示選自於下示之基團·· _(〇C2H4)nOH，其中η 為約2至約20之整數；氮係鍵結至選自於含至少4個碳原子 10 之烷基之至少兩個基團及芳基；以及磷及硫係鍵結至至少4 個氧原子。 較佳非離子性界面活性劑諸如八乙二醇一-十二烧基 醚(Ci2E〇8，其中ΕΟ表示環氧乙烧)及八乙二醇一_十六院基 醚(C^EO8)或含有相關分子混合物之商用產物係用作為有 15機結構導向劑。其它較佳有機結構導向劑包括環氧丙烷之 聚氧伸烷基衍生物，諸如以商品名「普龍尼克(piur〇nic)」 出售者及離子性界面活性劑諸如Ctab。 發現經由變更用作為結構導向劑之界面活性劑之煙鍵 長度，或經由以烴添加劑補充界面活性劑，可改變多孔材 20料之孔徑。舉例5之，較短鏈界面活性劑將導向較小孔徑 孔隙之形成’而較長鏈界面活性劑傾向於產生較大孔徑孔 隙。添加斥水烴添加劑諸如正庚院來補充用作為結構導向 劍之界面活性劑，相對於藉該界面活性劑於無添加劑存在 下所達成之孔徑，可增加孔徑。此外，煙添加劑可用來變 12 200835026 更液晶相之相結構，俾便控制多孔材料之相對應之規則結 構。經由此等方法之適當組合，比較先前所能達成者，可 極為精確且於寬廣範圍延伸至遠較小之孔徑（約為1奈米）控 制孔徑。 5 /容*1 丨係含括於混合物來溶解來源材料，以及與有機結 構f向知]組合形成液晶相，藉此來提供中孔材料之沉積介 質。通#使用水作為較佳溶劑。但於某些情況下，可能期 望或需要於非水性環境進行沉積。於此等情況下，可使用 適當有機溶劑，例如甲醯胺或乙二醇。 1° 於大部分情況下，來源材料將溶解於液晶相之溶劑領 域，但於某些情況下，來源材料將溶解於該液晶相之斥水 領域。 混合物視需要可進一步包括斥水烴添加劑來修改多孔 材料之孔隙直控，容後詳述。適當烴添加劑包括正庚烧、 15正十四烷、及三甲苯。烴添加劑可以相對於結構導向劑之 莫耳比於Ό.1至4且較佳於0.5至1之範圍存在於混合物。 另外，形成為中孔層之材料可藉無電沉積而沉積。用 於藉無電沉積製造材料之程序大致上係與前文說明用於化 學沉積之程序相同。主要差異為於施加液晶樣板至撐體 2〇前，撐體使用金屬鹽敏化來促進中孔材料只沉積於撑體表 面上，而非沉積遍布液晶。要言之，金屬鹽還原成為金屬 可藉恰如同化學沉積以適當還原劑協助。存在有敏化劑將 此沉積限於撐體表面。適當敏化劑為氯化錫(Π)。 多孔材料之規則孔隙結構例如可為立方體、層狀體、 13 200835026 斜體、面心矩形體、體心斜方體、體心四方體、斜方六面 體、或六方體。較佳規則孔隙結構為六方體。 本發明進—步係藉下列非限制性實例舉例說明。 比較例1 5 電沉積銅-錫 製備由〇·5Μ四氟肩酸錫(Π)、0.05M四氟酸銅(11)、 0·3Μ硼酸及0.3Μ四貌删酸所組成之水性鐘覆浴。7克 職-TX界面活性劑(得自尼可公司陳。1)}混合7克鑛覆 /口 /合液來形成均貝六方體(Η〇相。12微米銅箔於^ 水性 10氨洛液中洗滌，接著於〇.5M硫酸溶液洗務，隨後進行電沉 積。具有面積為10平方厘米之厚15毫米罩施用至銅箱，以 BC10-TX/鍍覆浴混合物填補。⑵微米錫箱計數器電極施用 至氏相。於相對於錫反電極為-0.03伏特進行恆電壓沉積至 通過3庫倫/平方厘米。然後沉積薄膜以2_丙醇洗滌來去除界 15 面活性劑。 比較例2 2〇°/〇孔隙度奈米多孔錮-媒粉木之盤備 72克BC10-TX界面活性劑加熱至熔融。於其中添加含 有12.0立方厘米0.3M甲磺酸錫(II)溶液(水性）、12·〇立方厘 20 米硫酸銅(Π)溶液(水性）、及0.63克次磷酸鈉於24立方厘米 去離子水之混合物。所得糊料激烈擾拌至均質，然後讓其 冷卻至室溫，讓其於室溫放置隔夜。透過於去離子水重複 洗滌，而由所得產物去除界面活性劑。 實例1 14 200835026 1_9%孔隙度奈米多孔铜-银粉夫之禦借 72克BC10-TX界面活性劑加熱至熔融。於其中添加人 有12.0立方厘米〇·6Μ甲磺酸錫(11)溶液（水性）、12 〇立方厘 米0.6Μ硫酸銅(II)溶液(水性）、及〇·42克二甲基胺_硼烷錯合 5物於24立方厘米去離子水之混合物。所得糊料激烈::: 均質，然後讓其冷卻至室溫，讓其於室溫放置隔夜。透過 於去離子水重複洗務，而由所得產物去除界面活性劑。藉 BET分析測定，發現平均孔徑為2·5奈米。 實例2 10 使用EPDM黏結劑之雷搞’诰 製備基於使用液晶樣板途徑所製造之奈米多孔銅-錫 之鋰離子電池組陽極。銅-錫材料由氮孔隙計量術(βετ)測 篁值求出具有孔隙度39%，且係如實例丨所述製備。銅_錫材 料首先混合由己烷及乙烯丙烯二烯單體(EPDM)所組成之 15溶液，隨後添加提卡(Timcal)KS-6石墨，故電極(於蒸發去 除己烷後）中之銅-錫、EPDM及石墨之百分比分別為9〇%、 5竓及5重里比。所得糊料展開於厚μ微米之銅箔上，其係 作為集電器，讓己烷蒸發，留下黏著於銅箔之 石墨複合物均勻塗層。 20 實例3 使用SBR/CMC黏結劑之電極盤浩 製備基於使用液晶樣板途徑所製造之奈米多孔銅_錫 之鋰離子電池組陽極。銅-錫材料由氮孔隙計量術(BET)測 量值求出具有孔隙度39%，且係如實例1所述製備。銅_錫材 15 200835026 料首先混合提卡KS-6石墨，隨後添加苯乙烯丁二稀橡膠 (SBR)及叛基甲基纖維素(CMC)之水性溶液，讓電極(於蒸發 去除水後）中之銅-鍚、SBR、CMC及石墨之百分比分別為 80%、6%、4%及10%重量比。所得糊料展開於厚14微米之 5銅箔上，其係作為集電器，讓水蒸發，留下黏著於銅箱之 銅-錫/SBR/CMC/石墨複合物均勻塗層。本複合電極隨後經 壓延來改良黏著性。 實例4 I用電沉積薄膜之雷池芻i告 10 具有腳印面積為丨·2平方厘米之鋰離子電池組係使用 自製電池殼體製造。陰極係由鋰箔所組成。陽極係由如比 車父例1所製備之液晶樣板化奈米多孔鋼_錫所組成。隔件係 由兩層瓦特曼(Whatman)玻璃纖維濾紙所組成，含有 UPF6於碳酸伸乙酯及碳酸二伸乙酯之混合物所組成之電 15解質（LP30色雷特普（Selectipur)，得自默克公司（Merck))。 一旦組裝妥，電池使用相對於Li/Li+之低電壓極限為〇〇〇5 伏特，及相對於Li/Li+之上限為1.3伏特，以放電深度， 以C/10速率循環。 a 實例5 20 炎用SBR/CMC結合電極之電池韻造 使用自製電池殼體，製造具有腳印面積為12平方厘米 之經離子電池組。如同業界標準，陰極係由uc〇〇2支载於 鋁上所組成。如實例3製備，陽極係由液晶樣板化奈米多孔 銅錫SBR/CMC及石墨沉積於銅羯上所組成。隔件係由兩 16 200835026 層席爾嘉(Celgard) 2400膜所組成，含有wMLipF6於碳酸 伸乙酯及碳酸二伸乙醋之混合物所組成之電解質(Lp3〇色 雷特普，得自默克公司）。链箱插置於兩層隔件間且係用作 為參考電極。-旦組裝妥，電池係使用對銅_錫複合電極而 5言，相對MLi/Li+之電壓極限為0.005伏特，以100%放電深 度，以C/10速率循環。 實例6 使用EPDM結合雷極之雷池_诰 使用自製電池殼體，製造具有腳印面積為12平方厘米 10之鋰離子電池組。如同業界標準，陰極係由LiCo〇2支栽於 鋁上所組成。如實例2製備，陽極係由液晶樣板化奈米多孔 銅_錫、EPDM及石墨沉積於銅箔上所組成。隔件係由兩層 席爾希2400膜所組成，含有由LiPF6於碳酸伸乙_及石山 酸二伸乙醋之混合物所組成之電解質（Lp3〇色雷特普，得自 15默克公司）。鋰箔插置於兩層隔件間且係用作為參考電槌。 一旦組裝妥，電池係使用2·5伏特電壓下限，以1〇〇%玫電深 度，以C/10速率循環。 【圖式簡單說明】 第1圖比較兩種電池之週期壽命表現；一者係如實例6 20 所述製備，另一者係使用相同構造，唯一差異為如比較例1 所述使用沉積材料(使用液晶樣板製成）。 【主要元件符號說明】 (無） 17Any suitable amphiphilic organic compound which can be used in the liquid crystal phase can be used as a structure directing agent, and the structure directing agent can be a low molar amount or a compound. Such structure directing agents include compounds which are occasionally referred to as organic directing agents. In order to provide the desired homogeneous liquid crystalline phase, the amphiphilic compound is typically employed at a high concentration, typically at least about 10% by weight, preferably at least 2% by weight, based on the total weight of the solvent, source material and amphiphilic compound. Preferably, and 20 is at least 30% by weight. Preferably, the organic structure directing agent comprises a compound RQ organic surfactant compound wherein R represents a linear or sub-fraction of from 6 to about 60 carbon atoms and preferably from 12 to 18 carbon atoms; And the Q table is not selected from the group shown below: [〇(CH2L]n〇H, wherein the claw is] to an integer of about 4 11 200835026 and preferably m is 2, and n is an integer from 2 to about 60 and Preferably 4 to 12; nitrogen is bonded to at least one selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and an alkylaryl group having at least 4 carbon atoms; and a sulfur bond is bonded thereto to At least 2 oxygen atoms. Other suitable structure directing agents include monosaccharides, phospholipids, 5 and glycolipids. Other suitable compounds include interfacially active organic compounds of the formula R!R2Q, where 1 and 112 represent 6 to about 36 An aryl group or an alkyl group of a carbon atom or a combination thereof; and Q represents a group selected from the group consisting of _(〇C2H4)nOH, wherein η is an integer from about 2 to about 20; and the nitrogen bond is selected from At least two groups and an aryl group having an alkyl group having at least 4 carbon atoms of 10; and phosphorus and a sulfur group bonded to at least 4 oxygen atoms. An active agent such as octaethylene glycol mono-dodecyl ether (Ci2E〇8, wherein ΕΟ represents epoxy bromide) and octaethylene glycol 1-6 hexyl ether (C^EO8) or a mixture of related molecules The commercial product is used as a 15 machine structure directing agent. Other preferred organic structure directing agents include polyoxyalkylene derivatives of propylene oxide, such as those sold under the trade name "piur〇nic" and ions. A sexual surfactant such as Ctab. It is found that the pore size of the porous material 20 can be changed by changing the length of the smoke bond used as the surfactant of the structure directing agent, or by supplementing the surfactant with the hydrocarbon additive. For example, the shorter chain The surfactant will direct the formation of smaller pore pores' while longer chain surfactants tend to produce larger pore sizes. Adding water repellent hydrocarbon additives such as Zheng Gengyuan to supplement the surfactant used as a structure-oriented sword, as opposed to By using the pore size of the surfactant in the absence of additives, the pore size can be increased. In addition, the smoke additive can be used to change the phase structure of the liquid crystal phase of 200835026, and the corresponding control of the porous material by the sputum Regular structure. By appropriate combination of these methods, it is possible to compare the previously achievable, extremely accurate and wide-range to a much smaller aperture (approximately 1 nm) control aperture. 5 /容*1 丨系系Included in the mixture to dissolve the source material, and combined with the organic structure f to form a liquid crystal phase, thereby providing a deposition medium for the mesoporous material. It is preferred to use water as the preferred solvent. However, in some cases, it may be desirable Or need to be deposited in a non-aqueous environment. In these cases, a suitable organic solvent such as formamide or ethylene glycol can be used. 1° In most cases, the source material will dissolve in the solvent field of the liquid crystal phase, but In some cases, the source material will dissolve in the water repellent field of the liquid crystal phase. The mixture may optionally include a water repellent hydrocarbon additive to modify the pore direct control of the porous material, as described in detail later. Suitable hydrocarbon additives include n-heptane, 15 n-tetradecane, and trimethylbenzene. The hydrocarbon additive may be present in the mixture in a molar ratio to the structure directing agent in the range of from 0.1 to 4 and preferably from 0.5 to 1. In addition, the material formed as the mesoporous layer can be deposited by electroless deposition. The procedure for making materials by electroless deposition is generally the same as the procedure described above for chemical deposition. The main difference is that before the application of the liquid crystal template to the support 2, the support is sensitized with a metal salt to promote the deposition of the mesoporous material only on the surface of the support, rather than depositing over the liquid crystal. In other words, the reduction of a metal salt to a metal can be assisted by chemical deposition with a suitable reducing agent. There is a sensitizer that limits this deposition to the surface of the support. A suitable sensitizer is tin chloride (ruthenium). The regular pore structure of the porous material may be, for example, a cube, a layered body, 13 200835026 italic, a face-centered rectangular body, a body-centered rhombohedron, a body-centered square, a rhombohedron, or a hexagonal body. Preferably, the regular pore structure is a hexagonal body. The invention is further illustrated by the following non-limiting examples. Comparative Example 1 5 Electrodeposition of copper-tin to prepare an aqueous clock consisting of 〇·5Μtetrahydrourethane (Π), 0.05 M copper tetrafluorolate (11), 0·3 Μboronic acid and 0.3 Μ tetramorphic acid bath. 7 grams of -TX surfactant (available from Nico Corporation. 1)} Mix 7 grams of mineral coating / mouth / liquid to form a hexagonal hexagonal body (Η〇 phase. 12 micron copper foil in ^ water 10 ammonia) The solution was washed in a liquid, followed by washing in a M5 M sulfuric acid solution, followed by electrodeposition. A 15 mm thick hood having an area of 10 cm 2 was applied to the copper box and filled with a BC10-TX/plating bath mixture. (2) Micron tin box The counter electrode was applied to the phase. Constant voltage deposition was carried out at -0.03 volts relative to the tin counter electrode to pass 3 coulombs per square centimeter. The deposited film was then washed with 2-propanol to remove the bound surfactant. Comparative Example 2 2 〇°/〇 Porosity Nanoporous Tantalum-Medium Powder Wood Plate 72 grams of BC10-TX surfactant is heated to melt. Add 12.0 cubic centimeters of 0.3M tin(II) methanesulfonate solution (aqueous), 12·〇 厘 20 米 20 m copper sulfate (Π) solution (aqueous), and 0.63 g of sodium hypophosphite in a mixture of 24 cm 2 deionized water. The resulting paste was vigorously disturbed to homogeneity, and then allowed to cool to room temperature, Let it sit overnight at room temperature. Repeat the washing through deionized water. The surfactant was removed. Example 1 14 200835026 1_9% Porosity Nanoporous Copper-Silver Powder was heated to melt by 72 g of BC10-TX surfactant. 12.0 cm3 of 〇·6Μmethanesulfonate was added to the person. (11) A solution of a solution (aqueous), 12 〇 cubic centimeter 0.6 Μ copper (II) sulfate solution (aqueous), and 42 42 g of dimethylamine borane conjugate 5 in 24 cc of deionized water. The resulting paste was intense::: homogenized, then allowed to cool to room temperature and allowed to stand overnight at room temperature. The washing was repeated by deionized water, and the surfactant was removed from the resulting product. The pore size is 2.5 nm. Example 2 10 Using a EPDM binder, a lithium-ion battery anode based on nanoporous copper-tin fabricated using a liquid crystal template approach was prepared. The copper-tin material was measured by nitrogen pores. The (βετ) enthalpy value was found to have a porosity of 39%, and was prepared as described in Example 铜. The copper-tin material was first mixed with a 15 solution consisting of hexane and ethylene propylene diene monomer (EPDM), followed by addition. Timcal KS-6 graphite, so the electrode (in evaporation The percentages of copper-tin, EPDM and graphite in the hexane-free process are 9〇%, 5竓 and 5 weight ratio respectively. The obtained paste is spread on copper foil with a thickness of μμm, which is used as a current collector. The alkane evaporates, leaving a uniform coating of the graphite composite adhered to the copper foil. 20 Example 3 Using a SBR/CMC binder electrode tray to prepare a nano-porous copper-tin-based lithium-ion battery pack based on the liquid crystal template approach Anode. The copper-tin material was found to have a porosity of 39% as determined by nitrogen porosimetry (BET) measurements and was prepared as described in Example 1. Copper_tin 15 200835026 Firstly mix the Tika KS-6 graphite, then add the aqueous solution of styrene butyl rubber (SBR) and mercaptomethyl cellulose (CMC), and let the electrode (after evaporation to remove water) The percentages of copper-bismuth, SBR, CMC and graphite in the medium are 80%, 6%, 4% and 10% by weight, respectively. The resulting paste was spread on a copper foil of 14 microns thick which was used as a current collector to evaporate water leaving a uniform coating of copper-tin/SBR/CMC/graphite composite adhered to the copper box. The composite electrode is then calendered to improve adhesion. Example 4 I. Electrodeposited film of the mine cell 10 The lithium ion battery pack having a footprint of 丨·2 cm 2 was fabricated using a self-made battery case. The cathode system is composed of a lithium foil. The anode was composed of a liquid crystal-coated nanoporous steel-tin prepared as in the first example of the vehicle. The spacer is composed of two layers of Whatman glass fiber filter paper, and contains 15 parts of UPF6 in a mixture of ethyl carbonate and diethyl carbonate to remove the substance (LP30 Color Selectipur). From Merck (Merck). Once assembled, the battery uses a low voltage limit of 〇〇〇5 volts relative to Li/Li+ and an upper limit of 1.3 volts relative to Li/Li+, circulating at a C/10 rate at the depth of discharge. a Example 5 20 Battery Synthetic with SBR/CMC Bonded Electrode An ionized battery pack with a footprint of 12 cm 2 was fabricated using a self-made battery case. As in the industry standard, the cathode system consists of uc〇〇2 supported on aluminum. Prepared as in Example 3, the anode consisted of liquid crystal-coated nanoporous copper-tin SBR/CMC and graphite deposited on copper matte. The separator consists of two 16 200835026 layers of Celgard 2400 membrane containing an electrolyte composed of a mixture of wMLipF6 in ethyl carbonate and diacetate (Lp3 雷色雷普, from Merck the company). The chain case is inserted between the two layers of the spacer and serves as a reference electrode. Once assembled, the battery was used with a copper-tin composite electrode, with a voltage limit of 0.005 volts relative to MLi/Li+, circulating at a C/10 rate at 100% discharge depth. Example 6 Using EPDM in combination with a thunderbolt pool _诰 A lithium ion battery pack having a footprint of 12 cm 2 was fabricated using a self-made battery case. As in the industry standard, the cathode system consists of LiCo〇2 branched on aluminum. Prepared as in Example 2, the anode consisted of liquid crystal-coated nanoporous copper-tin, EPDM and graphite deposited on copper foil. The separator consists of two layers of Schilsch 2400 membrane containing an electrolyte consisting of a mixture of LiPF6 in acetonitrile and ethanoic acid (Lp3 雷雷雷普, available from 15 Merck) . Lithium foil is inserted between the two layers of spacers and used as a reference. Once assembled, the battery is cycled at a C/10 rate using a lower voltage limit of 2.5 volts and a rake depth of 1%. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 compares the cycle life performance of two batteries; one is prepared as described in Example 6 20, the other using the same configuration, the only difference being the use of deposited materials as described in Comparative Example 1 ( Made using a liquid crystal template). [Main component symbol description] (none) 17