TWI689465B - Method for manufacturing carbon conductive coating - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
本發明係關於一種電化學領域，特別是關於一種碳導電層及其製備方法。 The invention relates to an electrochemical field, in particular to a carbon conductive layer and a preparation method thereof.
為了降低鋰電池內阻且延長鋰電池壽命，目前鋰電池所使用的集電體表面處理方式有兩種，一種是通過化學或物理的方式對集電體表面進行表面蝕刻，形成凹凸不平的粗糙表面，從而增加與電池漿料與集電體表面的接觸面積並增強附著力，但此方式工藝要求較高，且價格昂貴不利於大規模生產。另一方法是在集電體表面塗覆導電塗層。即利用導電漿料均勻塗佈於鋁箔或銅箔集電體表面形成導電塗層，再將電池漿料塗覆於導電塗層上，藉由集電體與導電塗層的物理接觸，將電化學反應產生的電子匯集並導出至外電路，實現化學能轉化為電能的過程。 In order to reduce the internal resistance of the lithium battery and extend the life of the lithium battery, there are two current surface treatment methods for the current collector used in the lithium battery. One is to etch the surface of the current collector by chemical or physical methods to form uneven roughness. Surface, thereby increasing the contact area with the battery paste and the surface of the current collector and enhancing adhesion, but this method requires high technology and is expensive and is not conducive to mass production. Another method is to apply a conductive coating on the collector surface. That is, the conductive paste is evenly coated on the surface of the aluminum foil or copper foil current collector to form a conductive coating, and then the battery slurry is coated on the conductive coating, and the physical contact between the current collector and the conductive coating will electrify The electrons generated by the chemical reaction are collected and exported to an external circuit to realize the process of converting chemical energy into electrical energy.
然而，集電體與電池漿料的活性材料間的接觸是影響鋰離子電池充放電性能的重要因素，在此過程中活性材料的體積會發生變化，體積的膨脹收縮會造成電池漿料的活性材料與集電體間的黏附力變差、接觸電阻變大，造成電容量大幅衰減。 However, the contact between the current collector and the active material of the battery slurry is an important factor affecting the charging and discharging performance of the lithium ion battery. During this process, the volume of the active material will change, and the expansion and contraction of the volume will cause the activity of the battery slurry The adhesion between the material and the current collector becomes worse, and the contact resistance becomes larger, which causes a large attenuation of the capacitance.
舉例來說，以碳矽複合材料作為活性材料塗佈於集電體銅箔上的導電塗層其膨脹率會較石墨高出許多，劇烈的體積膨脹收縮對會活性 材料產生機械應力，導致該電池漿料從集電體上剝離，使電極電容量迅速衰退。以及現有的導電塗層附著性不佳，製成導電漿料塗佈於集電體表面後所形成的導電塗層容易剝落，附著性不佳也會增加電池漿料與集電體間的界面電阻，製備成電池後會影響電池內阻。而導電塗層材料若選用金屬微粒或金屬包覆的聚合物顆粒，則會有成本太高、易氧化、導電塗層的漿料容易分層、不易施工等缺點。 For example, the conductive coating of carbon-silicon composite material as the active material coated on the copper foil of the current collector will have a much higher expansion rate than graphite, and the dramatic volume expansion and contraction will be active. The mechanical stress of the material causes the battery paste to peel off from the current collector, causing the electrode capacitance to decline rapidly. And the existing conductive coating has poor adhesion. The conductive coating formed after the conductive paste is coated on the surface of the current collector is easy to peel off. Poor adhesion will also increase the interface between the battery paste and the current collector Resistance, after being prepared into a battery, will affect the internal resistance of the battery. If the conductive coating material is selected from metal particles or metal-coated polymer particles, it will have the disadvantages of too high cost, easy oxidation, easy stratification of the conductive coating slurry, and difficulty in construction.
上述實現的技術描述在現有專利中，例如中華民國專利第I620372號揭露鋰離子蓄電池用負極材料，鋰離子蓄電池用負極及鋰離子蓄電池，鋰離子蓄電池用負極材料含有具備以下特性的碳材料：藉由X射線繞射法所求取之平均面間隔為0.335nm~0.340nm，體積平均粒徑為1μm~40μm，最大粒徑為74μm以下，以及在空氣氣流中的示差熱分析中，在300℃以上1000℃以下的溫度範圍內具有至少2個放熱峰值。然而，該習知技術提供的碳材料僅能達到提升充放電效率及熱安定性的功效，並無法解決導電塗層容易剝落的問題。 The technology described above is described in existing patents. For example, Republic of China Patent No. I620372 discloses negative electrode materials for lithium ion batteries, negative electrodes for lithium ion batteries, and lithium ion batteries. The negative electrode materials for lithium ion batteries contain carbon materials with the following characteristics: The average plane spacing determined by the X-ray diffraction method is 0.335 nm to 0.340 nm, the volume average particle size is 1 μm to 40 μm, the maximum particle size is 74 μm or less, and in differential thermal analysis in air flow, at 300°C There are at least 2 exothermic peaks in the temperature range above 1000°C. However, the carbon material provided by the conventional technology can only achieve the effects of improving charge and discharge efficiency and thermal stability, and cannot solve the problem that the conductive coating is easily peeled off.
再者，中華民國專利第I569502號揭露一種集電體，該種集電體藉由改善設置於集電體上的導電樹脂層表面與活性物質等的密合性，來提高使用了該種集電體的非水電解質電池、電雙層電容器或鋰離子電容器等的高速率特性或電極壽命。前案的集電體在導電性基材的至少單面上形成了具有導電性的樹脂層。該習知技術在集電體表面塗佈具有凹凸部表面的樹脂層，活性物質可以流入該凹凸部，增加電池漿料與集電體之間附著力。但是該習知技術為前述通過化學或物理的方式對集電體表面進行表面蝕刻以形成凹凸不平的粗糙表面的變化實施方式，樹脂層與電池漿料之 間的附著力情況仍存有疑慮。 Furthermore, Republic of China Patent No. I569502 discloses a current collector which improves the use of the current collector by improving the adhesion between the surface of the conductive resin layer provided on the current collector and the active material, etc. High-rate characteristics or electrode life of non-aqueous electrolyte batteries, electric double-layer capacitors, or lithium-ion capacitors. In the current collector of the foregoing case, a conductive resin layer is formed on at least one surface of the conductive base material. This conventional technique coats the surface of the current collector with a resin layer having an uneven surface, and the active material can flow into the uneven portion to increase the adhesion between the battery paste and the current collector. However, this conventional technique is the above-mentioned variation embodiment in which the current collector surface is chemically or physically etched to form an uneven rough surface, the resin layer and the battery paste There are still doubts about the adhesion between the two.
另外，美國專利US 9,437,344號揭露一種用作具有高導電能力的鋰二次電池負極材料的石墨或石墨-碳微粒。碳微粒由核心碳或石墨顆粒和多個分別與核心顆粒結合的衛星碳或石墨顆粒形成，其中核心顆粒為球形，形狀稍微延長並且其中衛星顆粒是盤狀，片狀或片狀的顆粒，每個顆粒包含具有晶體軸尺寸和橫向尺寸的石墨微晶，然而其也無法解決導電塗層容易剝落的問題。 In addition, US Patent No. 9,437,344 discloses a graphite or graphite-carbon particle used as a negative electrode material of a lithium secondary battery with high conductivity. The carbon particles are formed of core carbon or graphite particles and a plurality of satellite carbon or graphite particles respectively combined with the core particles, wherein the core particles are spherical, the shape is slightly elongated, and wherein the satellite particles are disc-shaped, flake-shaped or flake-shaped particles, each Each particle contains graphite crystallites with a crystal axis size and a lateral size, but it cannot solve the problem that the conductive coating is easily peeled off.
因此，為了符合產業上之需求，有需要開發一種導電性強，塗佈於鋰離子電池的電池漿料與銅箔集電體之間且能夠避免鋰離子電池的電池漿料與銅箔集電體剝離情形的碳導電層。 Therefore, in order to meet the needs of the industry, there is a need to develop a highly conductive, coated between the battery paste of the lithium ion battery and the copper foil current collector and can avoid the current collector of the battery paste and the copper foil of the lithium ion battery Carbon conductive layer in the case of bulk peeling.
習知鋰離子電池的集電體與電池漿料之間的黏附力不佳，另外，現有的導電漿料塗佈於集電體表面後形成的導電塗層容易自集電體表面剝落，造成電容量大幅衰減的缺點。並且現有的導電塗層與集電體間附著性不佳也會增加後續的電池漿料與集電體間的界面電阻，進而增加了鋰離子電池的電池電組，造成鋰離子電池效能降低。 It is known that the adhesion between the collector of the lithium ion battery and the battery paste is not good. In addition, the conductive coating formed after the existing conductive paste is coated on the surface of the collector is easy to peel off from the surface of the collector, resulting in Disadvantages of large capacity attenuation. In addition, the poor adhesion between the existing conductive coating and the current collector will also increase the interface resistance between the subsequent battery paste and the current collector, thereby increasing the battery pack of the lithium-ion battery, resulting in a decrease in the performance of the lithium-ion battery.
為了解決上述問題，本發明提供一種碳導電層之製備方法，包括：提供一碳材料、一黏著劑、一助導劑以及一添加劑；將該碳材料、該黏著劑、該助導劑以及該添加劑攪拌分散於一溶劑中；使用一球磨程序與一超音波震盪程序，依序研磨及混合分散於該溶劑中的該碳材料、該黏著劑、該助導劑以及該添加劑以得到一導電漿料；加入一偶聯劑至該導電漿料中；以及將該導電漿料塗佈於一集電體的一表面上，以於該集電體的 該表面上形成一碳導電層。 In order to solve the above problems, the present invention provides a method for preparing a carbon conductive layer, including: providing a carbon material, an adhesive, a guiding agent and an additive; the carbon material, the adhesive, the guiding agent and the additive Stir and disperse in a solvent; use a ball milling procedure and an ultrasonic oscillating procedure to sequentially grind and mix the carbon material, the adhesive, the guiding agent and the additive dispersed in the solvent to obtain a conductive paste Adding a coupling agent to the conductive paste; and coating the conductive paste on a surface of a current collector, so that the current collector A carbon conductive layer is formed on the surface.
在本發明一實施例中，該碳導電層具有一厚度為0.1微米至2微米。 In an embodiment of the invention, the carbon conductive layer has a thickness of 0.1 μm to 2 μm.
在本發明一實施例中，塗佈該碳導電層的該集電體具有一抗張強力為大於7.0 Kgf。 In an embodiment of the invention, the current collector coated with the carbon conductive layer has a tensile strength greater than 7.0 Kg f .
在本發明一實施例中，該偶聯劑為3-氨丙基三乙氧基矽烷(APTES)。 In an embodiment of the invention, the coupling agent is 3-aminopropyltriethoxysilane (APTES).
在本發明一實施例中，該偶聯劑選自於烷基矽烷偶聯劑、氨基矽烷偶聯劑、鏈烯基矽烷偶聯劑、環氧烷基矽烷偶聯劑以及烷基丙烯酰氧基矽烷偶聯劑所組成的群組中。 In an embodiment of the present invention, the coupling agent is selected from alkyl silane coupling agent, amino silane coupling agent, alkenyl silane coupling agent, epoxy alkyl silane coupling agent and alkyl acryloyloxy Based on silane coupling agent.
在本發明一實施例中，相對於100份重量百分比的導電漿料中的固體含量，碳材料含量為5份至85份重量百分比，黏著劑含量為5份至50份重量百分比，助導劑含量為1份至40份重量百分比，以及添加劑含量為1份至30份重量百分比。 In an embodiment of the present invention, the carbon material content is 5 parts to 85 parts by weight, the adhesive content is 5 parts to 50 parts by weight relative to the solid content in 100 parts by weight of the conductive paste, and the guide agent The content is 1 part to 40 parts by weight, and the additive content is 1 part to 30 parts by weight.
在本發明一實施例中，該碳材料可選自石墨或石墨烯。 In an embodiment of the invention, the carbon material may be selected from graphite or graphene.
在本發明一實施例中，該助導劑可選自以下所組成的群組中：奈米碳纖維、碳奈米管、乙炔黑、導電碳黑及鱗片狀石墨。 In an embodiment of the invention, the guiding agent may be selected from the group consisting of: nano carbon fiber, carbon nano tube, acetylene black, conductive carbon black, and flake graphite.
在本發明一實施例中，該黏著劑可選自以下所組成的群組中：聚偏氟乙烯(PVDF)、羧甲基纖維素鈉(CMC)、丁苯橡膠(SBR)及聚丙烯酸(PAA)，且該添加劑選自以下所組成的群組中：聚丙烯酸鈉、烷基苯磺酸鈉及硬脂酸鈉。 In an embodiment of the invention, the adhesive may be selected from the group consisting of polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR) and polyacrylic acid ( PAA), and the additive is selected from the group consisting of: sodium polyacrylate, sodium alkylbenzene sulfonate and sodium stearate.
在本發明一實施例中，該溶劑選自以下所組成的群組中： 水、乙醇、N-甲基吡咯酮(NMP)、甲苯及丙酮。 In an embodiment of the invention, the solvent is selected from the group consisting of: Water, ethanol, N-methylpyrrolidone (NMP), toluene and acetone.
為了解決上述問題，本發明另提供一種碳導電層，用於塗佈於一集電體的一表面，該碳導電層包括一導電漿料，該導電漿料由分散於一溶劑中的一碳材料、一黏著劑、一助導劑以及一添加劑構成；其中塗佈該碳導電層的該集電體具有一抗張強力為大於7.0 Kgf。 In order to solve the above problems, the present invention also provides a carbon conductive layer for coating on a surface of a current collector. The carbon conductive layer includes a conductive paste made of a carbon dispersed in a solvent Material, an adhesive, a guiding agent and an additive; wherein the current collector coated with the carbon conductive layer has a tensile strength greater than 7.0 Kg f .
在本發明一實施例中，該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑依序經由球磨與震盪後形成該導電漿料。 In an embodiment of the invention, the solvent, the carbon material, the adhesive, the guiding agent, and the additive are sequentially ball milled and shaken to form the conductive paste.
在本發明一實施例中，該碳導電層具有一厚度為0.1微米至2微米。 In an embodiment of the invention, the carbon conductive layer has a thickness of 0.1 μm to 2 μm.
在本發明一實施例中，該碳導電層更包括一偶聯劑。 In an embodiment of the invention, the carbon conductive layer further includes a coupling agent.
在本發明一實施例中，該偶聯劑為3-氨丙基三乙氧基矽烷(APTES)。 In an embodiment of the invention, the coupling agent is 3-aminopropyltriethoxysilane (APTES).
在本發明一實施例中，該偶聯劑選自於烷基矽烷偶聯劑、氨基矽烷偶聯劑、鏈烯基矽烷偶聯劑、環氧烷基矽烷偶聯劑以及烷基丙烯酰氧基矽烷偶聯劑所組成的群組中。 In an embodiment of the present invention, the coupling agent is selected from alkyl silane coupling agent, amino silane coupling agent, alkenyl silane coupling agent, epoxy alkyl silane coupling agent and alkyl acryloyloxy Based on silane coupling agent.
在本發明一實施例中，其中相對於100份重量百分比的導電漿料中的固體含量，碳材料含量為5份至85份重量百分比，黏著劑含量為5份至50份重量百分比，助導劑含量為1份至40份重量百分比，以及添加劑含量為1份至30份重量百分比。 In an embodiment of the present invention, with respect to the solid content in the conductive paste of 100 parts by weight, the carbon material content is 5 to 85 parts by weight, and the adhesive content is 5 to 50 parts by weight. The agent content is 1 part to 40 parts by weight, and the additive content is 1 part to 30 parts by weight.
在本發明一實施例中，該碳材料可選自石墨或石墨烯，並且該助導劑可選自以下所組成的群組中：奈米碳纖維、碳奈米管、乙炔黑、導電碳黑及鱗片狀石墨。 In an embodiment of the invention, the carbon material may be selected from graphite or graphene, and the guiding agent may be selected from the group consisting of: nano carbon fiber, carbon nano tube, acetylene black, conductive carbon black And flake graphite.
在本發明一實施例中，該黏著劑可選自以下所組成的群組中：聚偏氟乙烯(PVDF)、羧甲基纖維素鈉(CMC)、丁苯橡膠(SBR)及聚丙烯酸(PAA)，且該添加劑選自以下所組成的群組中：聚丙烯酸鈉、烷基苯磺酸鈉及硬脂酸鈉。 In an embodiment of the invention, the adhesive may be selected from the group consisting of polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR) and polyacrylic acid ( PAA), and the additive is selected from the group consisting of: sodium polyacrylate, sodium alkylbenzene sulfonate and sodium stearate.
為了解決上述問題，本發明另提供一種集電體，該集電體在至少一表面上形成有一如上所述的碳導電層。 In order to solve the above-mentioned problems, the present invention also provides a current collector having a carbon conductive layer as described above formed on at least one surface.
相較於習知鋰離子電池的集電體所使用的導電塗層，本發明提供的碳導電層及其製備方法，將碳材料、黏著劑、助導劑和添加劑配方分散於溶劑中，依序以球磨與超音波震盪的方式混合與分散，得到在溶劑中穩定分散的導電漿料。該導電漿料可塗佈於集電體表面，得到形成有該碳導電層的集電體。應用在鋰離子電池上時，再將一電池漿料層塗覆於該碳導電層的表面上，該碳導電層的作用為可增加電池漿料層與集電體間之附著性並減少脫落情形，還可以有效降低電池內阻，提升電池性能。 Compared with the conductive coating used in current collectors of lithium-ion batteries, the carbon conductive layer provided by the present invention and the preparation method thereof disperse the carbon material, adhesive, auxiliary agent and additive formulation in a solvent according to The order is to mix and disperse by ball milling and ultrasonic vibration to obtain a conductive paste that is stably dispersed in the solvent. The conductive paste can be applied to the surface of the current collector to obtain the current collector on which the carbon conductive layer is formed. When applied to a lithium ion battery, a battery paste layer is coated on the surface of the carbon conductive layer. The role of the carbon conductive layer is to increase the adhesion between the battery paste layer and the current collector and reduce shedding. The situation can also effectively reduce the internal resistance of the battery and improve the battery performance.
S01~S04‧‧‧步驟 S01~S04‧‧‧Step
10‧‧‧集電體 10‧‧‧collector
101‧‧‧表面 101‧‧‧Surface
20‧‧‧碳導電層 20‧‧‧Carbon conductive layer
40‧‧‧電池漿料層 40‧‧‧ battery paste layer
第1圖為本發明碳導電層製備方法的流程示意圖；第2圖為本發明碳導電層製備方法所製備的一碳導電層塗佈於一集電體的結構示意圖；第3圖為本發明碳導電層製備方法所製備的碳導電層塗佈於集電體後再塗佈電池漿料的結構示意圖；第4圖為構成本發明碳導電層的導電漿料示意圖；第5圖為本發明的碳導電層形成於集電體後經電子顯微鏡放大觀察的 示意圖；第6圖為本發明的碳導電層形成於集電體之拉伸試驗結果示意圖；以及第7圖為本發明的集電體和習知集電體之導電性測試結果比較示意圖。 Fig. 1 is a schematic flow chart of the method for preparing a carbon conductive layer of the present invention; Fig. 2 is a schematic structural view of a carbon conductive layer prepared by the method for preparing a carbon conductive layer of the present invention coated on a current collector; Fig. 3 is a present invention The structure diagram of the carbon conductive layer prepared by the method for preparing the carbon conductive layer is coated on the current collector and then coated with the battery slurry; FIG. 4 is a schematic diagram of the conductive slurry constituting the carbon conductive layer of the invention; FIG. 5 is the invention After the carbon conductive layer is formed on the current collector, it is enlarged and observed by an electron microscope FIG. 6 is a schematic diagram of the tensile test results of the carbon conductive layer of the present invention formed on the current collector; and FIG. 7 is a schematic diagram of the comparison of the electrical conductivity test results of the current collector and the conventional current collector of the present invention.
茲有關本發明之技術內容及詳細說明，現配合圖式說明如下：請參閱第1圖所示，第1圖為本發明碳導電層製備方法的流程示意圖。本發明提供一種碳導電層之製備方法，包括：步驟S01：提供一碳材料、一黏著劑、一助導劑以及一添加劑；步驟S02：將該碳材料、該黏著劑、該助導劑以及該添加劑分散於一溶劑中；步驟S03：提供一球磨程序與一超音波震盪程序，依序研磨及混合分散於該溶劑中的該碳材料、該黏著劑、該助導劑以及該添加劑以得到一導電漿料；步驟S04：加入一偶聯劑至該導電漿料中；以及步驟S05：將該導電漿料塗佈於一集電體的一表面上，以於該集電體的該表面上形成一碳導電層。 The technical content and detailed description of the present invention are now described in conjunction with the drawings as follows: Please refer to FIG. 1, which is a schematic flow chart of the method for preparing a carbon conductive layer of the present invention. The invention provides a method for preparing a carbon conductive layer, comprising: Step S01: providing a carbon material, an adhesive, a guiding agent and an additive; Step S02: the carbon material, the adhesive, the guiding agent and the The additives are dispersed in a solvent; step S03: providing a ball milling procedure and an ultrasonic oscillating procedure, sequentially grinding and mixing the carbon material, the adhesive, the guiding agent and the additive dispersed in the solvent to obtain a Conductive paste; step S04: adding a coupling agent to the conductive paste; and step S05: coating the conductive paste on a surface of a current collector to the surface of the current collector A carbon conductive layer is formed.
在本發明一實施例中，先後經由一濕式球磨程序與超音波震盪程序混合與分散該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑，進而形成該導電漿料。以下為本發明碳導電層詳細製備方法。 In an embodiment of the present invention, the solvent, the carbon material, the adhesive, the auxiliary agent, and the additive are mixed and dispersed through a wet ball milling process and an ultrasonic oscillating process, to form the conductive paste. The following is a detailed preparation method of the carbon conductive layer of the present invention.
導電漿料之製備 Preparation of conductive paste
在一例示性實施例中，將碳材料(KS6)、黏著劑(CMC)、助導劑(Super p)、該添加劑(例如表面活性劑(Sodium dodecyl sulfate，SDS))與溶劑(水)混合在一起，以高速攪拌的方式分散，之後放入一球磨容器中以該濕式球磨的方式進行球磨，接著將半成品漿料取出以超音波震盪處理即製 備完成。 In an exemplary embodiment, a carbon material (KS6), an adhesive (CMC), a conductivity aid (Super p), the additive (for example, surfactant (Sodium dodecyl sulfate, SDS)) and a solvent (water) are mixed Together, disperse with high-speed stirring, and then put into a ball mill container to perform ball milling in the wet ball milling mode, and then take out the semi-finished slurry and prepare it by ultrasonic vibration treatment Ready to complete.
其中，導電漿料的固體含量為1~40重量百分比，碳材料(KS6)含量為5至85重量百分比，黏著劑(CMC)含量為5至50重量百分比，助導劑(Super p)含量為1至40重量百分比，以及表面活性劑(SDS)含量為1至30重量百分比。 Among them, the solid content of the conductive paste is 1 to 40 weight percent, the carbon material (KS6) content is 5 to 85 weight percent, the adhesive (CMC) content is 5 to 50 weight percent, and the superconductor (Super p) content is 1 to 40 weight percent, and the surfactant (SDS) content is 1 to 30 weight percent.
具有該碳導電層的集電體之製備 Preparation of current collector with carbon conductive layer
此外更可加入一偶聯劑(例如3-氨丙基三乙氧基矽烷(APTES))至上述製備之導電漿料中，之後以刮刀塗佈的方式，將該導電漿料塗佈在已清潔之鋁箔集電體或銅箔集電體表面上，通過調整刮刀間隙和塗佈速度，形成的導電漿料厚度為1微米至100微米，再將塗佈有導電漿料的鋁箔集電體或銅箔集電體置於烘箱中進行一烘乾程序，烘乾溫度為100℃，即製備出具有該碳導電層的鋁箔集電體或銅箔集電體。 In addition, a coupling agent (such as 3-aminopropyltriethoxysilane (APTES)) can be added to the conductive paste prepared above, and then the conductive paste is coated on the On the surface of the clean aluminum foil collector or copper foil collector, the thickness of the conductive paste formed is 1 micron to 100 micrometers by adjusting the blade gap and the coating speed, and then the aluminum foil collector coated with the conductive paste Or the copper foil current collector is placed in an oven to perform a drying process, and the drying temperature is 100°C, that is, an aluminum foil current collector or a copper foil current collector having the carbon conductive layer is prepared.
另外，偶聯劑的種類可包括但不限於為烷基矽烷偶聯劑、氨基矽烷偶聯劑、鏈烯基矽烷偶聯劑、環氧烷基矽烷偶聯劑和烷基丙烯酰氧基矽烷偶聯劑。其中該偶聯劑(APTES)可同時與集電體和碳導電層表面的無機官能基團發生鍵結，有效改善碳導電層與集電體間之界面相互作用力，使碳導電層與集電體間之界面黏結強度得到明顯的提升，詳細測試結果將如後述。 In addition, the type of coupling agent may include, but is not limited to, alkyl silane coupling agent, amino silane coupling agent, alkenyl silane coupling agent, epoxy alkyl silane coupling agent and alkyl acryloyloxy silane Coupling agent. Among them, the coupling agent (APTES) can simultaneously bond with the inorganic functional groups on the surface of the current collector and the carbon conductive layer, effectively improve the interface interaction force between the carbon conductive layer and the current collector, and make the carbon conductive layer and the collector The interfacial bonding strength between the electrical bodies has been significantly improved. The detailed test results will be described later.
請參閱第2圖所示，第2圖為本發明的一碳導電層塗佈於一集電體的結構示意圖。本發明提供一種碳導電層20，用於塗佈於一集電體10的一表面101，該碳導電層20包括一導電漿料，該導電漿料由分散於一溶劑中的一碳材料、一黏著劑、一助導劑以及一添加劑構成；其中塗佈該碳導
電層20的該集電體10具有一抗張強力為大於7.0 Kgf。
Please refer to FIG. 2, which is a schematic diagram of a carbon conductive layer coated on a current collector according to the present invention. The present invention provides a
該集電體10可為一鋁箔或一銅箔，作為鋰電池內的正負極材料。該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑經由球磨與震盪後形成該導電漿料，該導電漿料可在溶劑(例如水)中穩定分散長達三個月，該導電漿料塗佈於該鋁箔或該銅箔的其中一表面101或兩個表面101上形成該碳導電層，形成的該碳導電層具有一厚度為0.1微米至2微米。
The
其中，該碳材料可選自石墨或石墨烯。助導劑可選自奈米碳纖維、碳奈米管、乙炔黑、導電碳黑、鱗片狀石墨所組成的群組中。黏著劑可選自聚偏氟乙烯(PVDF)、羧甲基纖維素鈉(CMC)、丁苯橡膠(SBR)、聚丙烯酸(PAA)所組成的群組中。添加劑可選自聚丙烯酸鈉、烷基苯磺酸鈉、硬脂酸鈉。溶劑可為水、乙醇、N-甲基吡咯酮(NMP)、甲苯、丙酮所組成的群組中。但不以此為限。 Wherein, the carbon material may be selected from graphite or graphene. The guiding agent may be selected from the group consisting of nano carbon fiber, carbon nano tube, acetylene black, conductive carbon black, and flake graphite. The adhesive may be selected from the group consisting of polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), and polyacrylic acid (PAA). The additive may be selected from sodium polyacrylate, sodium alkylbenzene sulfonate, and sodium stearate. The solvent may be in the group consisting of water, ethanol, N-methylpyrrolidone (NMP), toluene, and acetone. But not limited to this.
在本發明一實施例中，依序經由一濕式球磨程序與一超音波震盪程序混合與分散該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑，進而形成該導電漿料。即先將該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑經由一濕式球磨程序得一半成品，再將該半成品經由超音波震盪程序分散該溶劑、該碳材料、該黏著劑、該助導劑以及該添加劑而形成該導電漿料。 In an embodiment of the present invention, the solvent, the carbon material, the adhesive, the guiding agent, and the additive are mixed and dispersed sequentially through a wet ball milling procedure and an ultrasonic oscillating procedure to form the conductive paste . That is, the solvent, the carbon material, the adhesive, the guiding agent, and the additive are first subjected to a wet ball milling process to obtain a semi-finished product, and then the semi-finished product is dispersed through the ultrasonic vibration process to the solvent, the carbon material, and the adhesion Agent, the guiding agent and the additive to form the conductive paste.
製備出之碳導電層具有良好的親水性、導電性、高比表面積、抗腐蝕和氧化，進而減少後續鋰電池的電池漿料與集電體10間的界面電阻。如第3圖中本發明碳導電層塗佈於集電體後再塗佈電池漿料的結構所示，圖中的集電體10塗佈了上述實施例的碳導電層20後，再於碳導電層20
的表面塗佈應用於上述鋰電池的一電池漿料層40，碳導電層20增加形成於集電體10的表面101的電池漿料層40與集電體10之間的接觸面積，並增加電池漿料層40與集電體10間的相互作用力，避免電池漿料層40容易自集電體10發生剝離脫落或是溶解的情況。在後續使用該集電體10於鋰電池充電放電的過程中，不會發生電池漿料層40與集電體10剝離或是溶解的情形。
The prepared carbon conductive layer has good hydrophilicity, conductivity, high specific surface area, corrosion resistance and oxidation, thereby reducing the interface resistance between the battery paste of the subsequent lithium battery and the
實驗例 Experimental example
將0.025克的黏著劑(CMC)與溶劑(水)在室溫下混合，該黏著劑為一親水性材料構成，但不限於此。混合後室溫下攪拌1小時，加入0.01克添加劑(例如表面活性劑(SDS))以及0.015克助導劑(Super p)後於室溫下攪拌20分鐘，將所得的一中間溶液倒入一球磨容器中並加入一碳源(即碳材料)，該碳源為0.05克的KS6，加入該碳源的中間溶液以500r.p.m的轉速進行濕式球磨3小時，之後再進行超音波震盪3小時，得到該導電漿料。在塗佈至集電體表面上前再加入0.1毫升的偶聯劑即可於該集電體的表面上塗佈形成該碳導電層。
0.025 grams of adhesive (CMC) and solvent (water) are mixed at room temperature. The adhesive is composed of a hydrophilic material, but it is not limited thereto. After mixing, stir at room temperature for 1 hour, add 0.01 g of additives (such as surfactant (SDS)) and 0.015 g of adjuvant (Super p), and stir at room temperature for 20 minutes. Pour the resulting intermediate solution into a Add a carbon source (that is, carbon material) to the ball mill container. The carbon source is 0.05 g of KS6. The intermediate solution added to the carbon source is subjected to wet ball milling at 500 r.pm for 3 hours, followed by
鑑定與測試 Identification and testing
如第4圖所示，其為構成本發明碳導電層的導電漿料示意圖。以上述製備方法製備完成的導電漿料靜置三個月之後未出現分層的現象，表示導電漿料混和均勻、穩定性佳。 As shown in FIG. 4, it is a schematic diagram of the conductive paste constituting the carbon conductive layer of the present invention. The conductive paste prepared by the above preparation method does not show delamination after being left for three months, indicating that the conductive paste is uniformly mixed and has good stability.
如第5圖所示，其為本發明的碳導電層形成於集電體後經電子顯微鏡放大觀察的示意圖，其中(A)部分為低倍率電子顯微鏡放大觀察的碳導電層，(B)部分為高倍率電子顯微鏡放大觀察的碳導電層。將導電漿料塗佈於銅箔集電體上，製備成塗碳銅箔。可觀察出銅箔集電體上覆蓋一層 均勻且緻密的碳導電層，並且碳導電層覆蓋情形良好沒有出現銅箔集電體裸露的情形，片狀之碳導電層緊密的貼附在銅箔集電體上。形成有碳導電層的銅箔集電體經由膠帶剝離測試後，膠帶並未將碳導電層自銅箔集電體黏貼起，碳導電層還是完整的附著在銅箔集電體表面上，附著力測試等級為0級，表示碳導電層對於銅箔集電體的黏附性極佳。 As shown in FIG. 5, it is a schematic view of the carbon conductive layer of the present invention after being formed on a current collector and enlarged and observed by an electron microscope, where part (A) is a carbon conductive layer magnified and observed by a low-power electron microscope, and part (B) It is a carbon conductive layer magnified and observed by a high-power electron microscope. The conductive paste is coated on the copper foil current collector to prepare a carbon coated copper foil. Observe that the copper foil collector is covered with a layer The carbon conductive layer is uniform and dense, and the carbon conductive layer is well covered without the exposed copper foil collector. The sheet-like carbon conductive layer is closely attached to the copper foil collector. After the copper foil current collector with the carbon conductive layer formed was peeled off by the tape, the tape did not stick the carbon conductive layer from the copper foil current collector. The carbon conductive layer was still completely attached to the surface of the copper foil current collector. The force test level is 0, indicating that the carbon conductive layer has excellent adhesion to the copper foil current collector.
如第6圖所示，其為本發明的碳導電層形成於集電體之拉伸試驗結果示意圖。拉伸試驗結果顯示形成有碳導電層的銅箔集電體的抗張強力約為7.0 Kgf，較未形成有碳導電層的銅箔的抗張強力6.8 Kgf為佳，且形成有碳導電層的銅箔集電體在180°折彎下，碳導電層並未剝離也無粉體掉落，表示碳導電層緊密的附著在銅箔集電體上。之後在鋰電池電極片輾壓的製程中，不會有破裂和脫落之情形發生。 As shown in FIG. 6, it is a schematic diagram of the tensile test results of the carbon conductive layer of the present invention formed on the current collector. The tensile test results show that the tensile strength of the copper foil collector with the carbon conductive layer is about 7.0 Kg f , which is better than the tensile strength of 6.8 Kg f of the copper foil without the carbon conductive layer, and the carbon is formed When the copper foil current collector of the conductive layer is bent at 180°, the carbon conductive layer is not peeled off and no powder is dropped, indicating that the carbon conductive layer is closely attached to the copper foil current collector. Afterwards, during the rolling process of the lithium battery electrode sheet, there will be no cracking or falling off.
此外，將塗碳銅箔浸泡於極性與非極性溶劑中，並以超音波震盪處理20分鐘，結果顯示在各溶劑中皆無任何剝落情形，而且靜置八個月後依然保持原樣，表示對各種溶劑的耐受性效果佳，碳導電層附著於銅箔集電體上之附著性能良好並且未有溶解的情形，如此後續選用鋰電池的電池漿料的種類選擇不會因為碳導電層在溶劑中會剝離而受限。 In addition, the carbon-coated copper foil was immersed in polar and non-polar solvents and treated with ultrasonic vibration for 20 minutes. The results showed that there was no peeling in each solvent, and it remained the same after eight months of standing. The solvent resistance effect is good, the adhesion of the carbon conductive layer to the copper foil collector is good and there is no dissolution, so the type of battery paste used for the subsequent selection of lithium batteries will not be selected because the carbon conductive layer is in the solvent Medium will be stripped and restricted.
最後，如第7圖所示，其為本發明的集電體和習知集電體之導電性測試結果比較示意圖。以習知的集電體(即裸銅箔)與本發明的集電體(即集電體表面上形成有碳導電層)分別用於製備純碳鋰離子電池，測試製備而得的兩種鋰離子電池在初始與1C倍率下循環40圈後之交流阻抗，從第7圖中可以看出本發明的集電體製成的鋰離子電池相對於習知的集電體製成的鋰離子電池具有較低的電池內阻。 Finally, as shown in FIG. 7, it is a schematic diagram comparing the results of the electrical conductivity test of the current collector of the present invention and the conventional current collector. The conventional current collector (ie, bare copper foil) and the current collector of the present invention (ie, a carbon conductive layer formed on the surface of the current collector) were used to prepare pure carbon-lithium ion batteries, respectively. The AC impedance of the lithium ion battery after 40 cycles at the initial and 1C rate can be seen from Figure 7 that the lithium ion battery made of the current collector of the present invention is compared to the lithium ion battery made of the conventional current collector. The battery has a low battery internal resistance.
綜上所述，本發明提供的碳導電層及其製備方法，將碳材料、黏著劑、助導劑和添加劑配方分散於溶劑中，以濕式球磨與超音波震盪的方式混合與分散，得到在溶劑中穩定分散的導電漿料。該導電漿料塗佈於集電體表面，得到形成有該碳導電層的集電體。將該集電體應用在鋰離子電池上，可增加後續電池漿料層與集電體間之附著性減少脫落情形，還可以有效降低電池內阻，提升電池性能。並且以本發明提供的碳導電層的製備方法製備出之碳導電層具有良好的親水性、導電性、高比表面積、抗腐蝕和氧化，進而減少後續電池漿料層與集電體間的界面電阻。碳導電層會增加集電體表面的電池漿料層與集電體之間的接觸面積，使電池漿料層與集電體之間相互作用力強，避免電池漿料層自集電體表面脫落，在鋰電池充放電的過程中，不會發生電池漿料層與集電體剝離或電池漿料層溶解的情形。 In summary, the carbon conductive layer and its preparation method provided by the present invention disperse carbon materials, adhesives, guide agents and additive formulations in a solvent, and mix and disperse them by wet ball milling and ultrasonic vibration to obtain Conductive paste stably dispersed in a solvent. The conductive paste is applied on the surface of the current collector to obtain the current collector on which the carbon conductive layer is formed. Applying the current collector to a lithium ion battery can increase the adhesion between the subsequent battery slurry layer and the current collector to reduce shedding, and can also effectively reduce the internal resistance of the battery and improve battery performance. Moreover, the carbon conductive layer prepared by the method for preparing a carbon conductive layer provided by the present invention has good hydrophilicity, conductivity, high specific surface area, corrosion resistance and oxidation, thereby reducing the interface between the subsequent battery slurry layer and the current collector resistance. The carbon conductive layer will increase the contact area between the battery paste layer on the surface of the current collector and the current collector, make the interaction force between the battery paste layer and the current collector strong, and avoid the battery paste layer from the surface of the current collector Shedding, in the process of charging and discharging of the lithium battery, there will be no peeling of the battery slurry layer from the current collector or dissolution of the battery slurry layer.
所屬領域之技術人員當可了解，在不違背本發明精神下，依據本發明實施態樣所能進行的各種變化。因此，顯見所列之實施態樣並非用以限制本發明，而是企圖在所附申請專利範圍的定義下，涵蓋於本發明的精神與範疇中所做的修改。 Those skilled in the art should understand that various changes can be made according to the implementation of the present invention without departing from the spirit of the present invention. Therefore, it is obvious that the listed embodiments are not intended to limit the present invention, but are intended to cover the modifications made in the spirit and scope of the present invention under the definition of the scope of the attached patent application.
S01~S05‧‧‧步驟 S01~S05‧‧‧Step
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| CN113381057A (en) * | 2021-06-07 | 2021-09-10 | 芜湖天弋能源科技有限公司 | High-safety lithium ion battery and preparation method thereof |
| WO2024000560A1 (en) * | 2022-07-01 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Conductive paste, current collector, secondary battery, battery module, battery pack and electric apparatus |
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| CN106328256A (en) * | 2016-10-28 | 2017-01-11 | 济宁利特纳米技术有限责任公司 | Conductive slurry for lithium ion battery and preparation method of conductive slurry |
| CN109192923A (en) * | 2018-09-25 | 2019-01-11 | 清华大学 | A kind of preparation method of negative electrode of lithium ion battery electrocondution slurry |
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| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN106328256A (en) * | 2016-10-28 | 2017-01-11 | 济宁利特纳米技术有限责任公司 | Conductive slurry for lithium ion battery and preparation method of conductive slurry |
| CN109192923A (en) * | 2018-09-25 | 2019-01-11 | 清华大学 | A kind of preparation method of negative electrode of lithium ion battery electrocondution slurry |
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| CN113381057A (en) * | 2021-06-07 | 2021-09-10 | 芜湖天弋能源科技有限公司 | High-safety lithium ion battery and preparation method thereof |
| WO2024000560A1 (en) * | 2022-07-01 | 2024-01-04 | 宁德时代新能源科技股份有限公司 | Conductive paste, current collector, secondary battery, battery module, battery pack and electric apparatus |
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