WO2012167407A1 - 一种铝箔预涂纳米导电碳底涂液的配置及其涂敷的方法 - Google Patents

一种铝箔预涂纳米导电碳底涂液的配置及其涂敷的方法 Download PDF

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WO2012167407A1
WO2012167407A1 PCT/CN2011/001140 CN2011001140W WO2012167407A1 WO 2012167407 A1 WO2012167407 A1 WO 2012167407A1 CN 2011001140 W CN2011001140 W CN 2011001140W WO 2012167407 A1 WO2012167407 A1 WO 2012167407A1
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nano
primer
binder
aluminum foil
oily
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French (fr)
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丁建民
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JIANGSU LENENG BATTERY Inc Co
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JIANGSU LENENG BATTERY Inc Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of lithium ion battery undercoating, in particular to a method for arranging and coating a primer solution in a primer layer of a lithium iron phosphate cathode material.
  • Lithium iron phosphate is a new type of energy storage battery developed in recent years, and it has become a new type of power battery with its advantages of safety performance, long cycle life and environmental friendliness.
  • the lithium iron phosphate primary particle diameter is generally between 10 nm and 2000 nm, the contact with the surface of the aluminum foil is point contact, and the lithium iron phosphate active material is poorly bonded to the current collector aluminum foil, resulting in an increase in the internal resistance of the battery and its polarization.
  • Gravure transfer coating and spraying technology is a new technology developed in recent years. Applying a thin layer of conductive coating on the current collector can increase the adhesion between the coating layer and the aluminum foil, and increase the coating layer. Adhesion of lithium iron phosphate active substance.
  • the choice of conductive adhesive is very important, and it has good adhesion to aluminum foil, good adhesion to lithium iron phosphate positive electrode paste, and good electrical conductivity. Since the conductive adhesive is mainly composed of a binder and a conductive agent, the binder property and the conductive agent are selected in consideration of the bonding property of the binder, and the particle diameter of the conductive agent is considered, so that the conductive agent is just right. The inside of the gap between the lithium iron phosphate particles, the aluminum foil and the lithium iron phosphate particles is sandwiched, and the internal resistance between the lithium iron phosphate and the aluminum foil is lowered.
  • the object of the present invention is to provide an arrangement of a primer solution for improving the rate of lithium iron phosphate battery, cycle performance, and reducing internal resistance of a battery, and a coating method thereof, which can greatly improve the activity of lithium iron phosphate.
  • an aluminum foil pre-coated nano-conductive carbon primer solution in terms of mass percentage, comprising the following steps: 1) configuring a primer solution; 2) ultrasonic dispersion; 1), Configure the primer solution:
  • the binder A is a crosslinked polymer of acrylic acid and acrylonitrile, and its molecular weight is 2000 ⁇ Between 30000.
  • the aqueous solvent is double distilled water or alcohol or IPA at a concentration of 10% to 95%.
  • the powder nano-conducting carbon composite conductive agent is mixed with the binder A in a ratio of 0.1 to 0.6:1.
  • the nano-conductive carbon composite conductive agent is a composite of nano-conductive carbon and Spper P in a ratio of 10:1 to 5, and the nano-conductive carbon used has a particle diameter of 10 nm to 1000 nm.
  • the binder B is polyvinylidene fluoride (PVDF), and the oil solvent having a molecular weight of 100-1.1 million is NMP, and the solvent purity is more than 98%.
  • PVDF polyvinylidene fluoride
  • the powder nano-conducting carbon composite conductive agent and binder B are mixed at a ratio of 1:0.1-0.8.
  • the nano-conducting carbon composite conductive agent is a composite of nano-conductive carbon and Spper P in a ratio of 10:1 to 5, and the nano-conductive carbon has a diameter of 10 nm to 1000 nm.
  • a primer solution having a viscosity of 200 to 20,000 cps was finally obtained by the above two methods.
  • the invention relates to a method for coating an aluminum foil pre-coated nano conductive carbon primer liquid, which is characterized in that the above-mentioned configured aqueous or oily primer liquid is sieved through a lu filter sieve, and is transferred by gravure coating or spray coating technology.
  • the battery prepared by the invention has small internal resistance, strong adhesion, good electrical conductivity and large compaction density, and has obvious effects especially for large-rate discharge of the battery. According to the requirements of the battery design, different thicknesses of the conductive current collector are applied according to the viscosity of the primer liquid, thereby improving the different performance of the battery.
  • Figure 1 is a graph showing the internal resistance of Battery A of the present invention.
  • Fig. 2 is a graph showing the voltage-discharge capacity magnification of the battery A.
  • nano-conductive carbon composite conductive agent is a mixture of 20 grams of nano-conductive carbon and 5 grams of Supper P composite conductive agent. The combination of nano-conducting carbon and Spper P not only increases the conductivity of the primer solution, but also improves the flatness of the coated surface.
  • the nano-conductive carbon composite conductive agent here is a mixture of 15 grams of nano-conductive carbon and 3 grams of Supper P composite conductive agent.
  • the aqueous solvent is double distilled water or alcohol/IPA at a concentration of 10% to 80%. Since the distilled water or alcohol, IPA contains a hydroxyl group, it is better compatible with the hydroxyl group in the binder.
  • the aqueous binder A is a binder having a concentration of 15% of acrylic acid and acrylonitrile to form a crosslinked polymer having a molecular weight of from 2,000 to 30,000.
  • the use of acrylic acid and acrylonitrile to form a crosslinked polymer as a binder and its molecular weight allows for better adhesion between the binder and the aluminum foil, the binder and the lithium iron phosphate active material.
  • Example 3 The configuration of the aluminum foil pre-coated nano-conductive carbon oil primer solution, in terms of mass percentage.
  • N-methylpyrrolidone NMP with a purity of more than 98% as an oil solvent and 35 g of polyvinylidene fluoride PVDF as binder B, and mechanically stir for 6 hours under high-speed stirring to obtain uniform and stable Binder system; then add 20g (total mass of 60g) powder nano-conducting carbon composite conductive agent system every 30 minutes, and then ultrasonically disperse for 2 hours, and finally add 300g NMP adjustment. Viscosity, and finally an oily primer solution with a viscosity of 3000 cps.
  • the nano-conductive carbon composite conductive agent is a mixture of 10 grams of nano-conducting carbon and 5 grams of Supper P composite conductive agent.
  • the binder B is selected from polyvinylidene fluoride (PVDF), and the molecular weight thereof is between 100 and 1.1 million.
  • the oil solvent is NMP, and the solvent purity is greater than 98% to make the binder and the aluminum foil, the binder and the iron phosphate. Better adhesion between lithium actives.
  • the configuration of the aluminum foil pre-coated nano-conductive carbon oil primer solution in terms of mass percentage.
  • Nmethylpyrrolidone NMP with a purity of more than 98% as an oil solvent and 30 g of polyvinylidene fluoride PVDF as a binder B, and mechanically stir for 5 hours under high-speed stirring to obtain a uniform and stable viscosity.
  • the bonding system afterwards, 66 g (total mass 198 g) of powder nano-conducting carbon composite conductive agent system was added every three minutes, and ultrasonic ultrasonic dispersion was used for 1 hour, and finally the mass was adjusted to 800 g NMP to adjust the viscosity. Finally, an oily primer solution having a viscosity of 2000 cps was obtained.
  • the nano-conductive carbon composite conductive agent is a mixture of 7 grams of nano-conductive carbon and 4 grams of Supper P composite conductive agent.
  • the nano-conducting carbon has a particle diameter of 10 nm to 100 nm; and the use of the nano-conductive carbon in combination with the Spper P not only increases the conductivity of the primer solution, but also improves the flatness of the coated surface.
  • the invention discloses a method for coating an aluminum foil pre-coated nano-conductive carbon primer liquid, which is obtained by using the lii filter sieve after being sieved by a lii filter sieve, and then coating by a gravure transfer or spraying by a spray coating technique. It is applied on the surface of aluminum foil, and its thickness is (0.1 ⁇ 10) ⁇ ⁇ . After drying, it is coated with lithium iron phosphate cathode material on its surface, and artificial graphite is used as anode material, using LiPF6/EC+DEC, volume ratio 1 : 1 is the electrolyte, Celgard 2400 membrane is the diaphragm, and 5AH soft pack battery is prepared.
  • the purpose is to increase the contact area of the lithium iron phosphate active material and the current collector, too thin to increase the contact area, too thick will reduce the volume energy of the single cell, affecting Electricity The overall performance of the pool.
  • the primer solution of the present invention is not applied on the surface of the aluminum foil, and the aluminum foil is used as a current collector, and the thickness thereof is (0.1 to 10) ⁇ ⁇ , lithium iron phosphate is used as a positive electrode material, and artificial graphite is used as a negative electrode material, and LiPFe/ is used.
  • the EC+DEC volume ratio of 1:1 was the electrolyte, and the Celgard 2400 membrane was the separator.
  • the 5AH soft pack battery B was prepared as a comparative battery.
  • Fig. 1 the battery is tested for the relationship between the DC internal resistance and the discharge capacity percentage of Battery A and Battery B under the condition of 10% discharge per charge, and the DC internal resistance-discharge capacity percentage curve is obtained. It can be seen from the figure that after applying the undercoat layer on the surface of the current collector aluminum foil, the DC internal resistance (average value of 3 ⁇ ⁇ ) is significantly reduced, which is significantly better than the DC internal resistance of the uncoated battery (average value is 5 ⁇ ⁇ ), and the DC internal resistance fluctuation of the battery is also better than the DC internal resistance of the uncoated battery.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

一种铝箔预涂纳米导电碳底涂液的配制方法及其涂敷方法，该配制方法包括以下步骤：1）配制水性或油性底涂液，其中水性底涂液包括水性溶剂1份，粘结剂A0.05-0.6份，粉体纳米导电复合导电剂0.05-0.6份；油性底涂液包括油性溶剂1份，粘结剂B0.03-0.6份，粉体纳米导电复合导电剂0.03-0.6份；2）超声波分散。通过涂敷该底涂液得到的电池内阻小、粘附力强、导电性好、压实密度大。

Description

一种铝箔预涂纳米导电碳底涂液的配置及其涂敷的方法 技术领域
本发明涉及锂离子电池底涂层技术领域，具体涉及一种磷酸铁锂正极材料的 底涂层中底涂液的配置与涂敷的方法。
背景技术
磷酸铁锂是近几年发展起来的一种新型储能电池，并以其安全性能髙、循环 寿命长、环境友好等优点成为一种新型动力电池。但是由于磷酸铁锂的导电性较 差，需要在磷酸铁锂中掺杂一些导电剂来改善其材料的导电性能，并提高其活性 材料间离子的导电性能，而对活性材料与集流体铝箔的导电性能并未改善。由于 磷酸铁锂一次粒子颗粒直径一般在 10nm〜2000nm之间，其与铝箔表面的接触是 点接触,磷酸铁锂活性材料与集流体铝箔粘结差，造成电池的内阻及其极化增加， 并影响到电池的倍率性能、循环性能。凹版转移涂敷与喷涂技术是近几年发展起 来新型技术，在集流体上涂敷一薄层导电涂敷层，既能增加涂敷层与铝箔的粘附 力， 又能增加涂敷层与磷酸铁锂活性物质的粘附力。 而导电胶的选择非常重要， 既要具有与铝箔好的粘附力，又要具有与磷酸铁锂正极浆料好的粘附力， 同时具 有好的导电性。由于导电胶主要由粘结剂与导电剂组成， 因此在选择粘结剂和导 电剂时既要考虑到粘结剂的粘结性能，又要考虑到导电剂的颗粒直径，做到导电 剂刚好夹在磷酸铁锂颗粒、铝箔、磷酸铁锂颗粒之间的空隙里面， 降低磷酸铁锂 与铝箔间的内阻。
发明内容
针对以上不足，本发明的目的在于提供一种提高磷酸铁锂电池倍率、循环性 能、降低电池内阻的底涂层中底涂液的配置及其涂敷方法，可以大幅度提高磷酸 铁锂活性物质与集流体之间的粘附力。
本发明的技术方案是通过以下方式实现的：一种铝箔预涂纳米导电碳底涂液 的配置， 以质量百分比计， 包括以下步骤： 1 )配置底涂液 ； 2)超声波分散； 1 )、 配置底涂液：
( 1 )水性底涂液的配置； 水性溶剂 1份、粘结剂 A 0.05〜0.6份、粉体纳米导电 碳复合导电剂 0.05~0.6份。
所述的粘结剂 A是丙烯酸与丙烯氰形成交联聚合物， 其分子量为 2000〜 30000之间。
所述的水性溶剂为二次蒸馏水或浓度为 10%~95%的酒精或 IPA。
所述的粉体纳米导电碳复合导电剂与粘结剂 A以 0.1〜0.6： 1的比例混合而 成。
所述的纳米导电碳复合导电剂是由纳米导电碳与 Spper P以 10: 1〜5的比 例复合而成， 所用纳米导电碳的粒径为 10nm— 1000nm。
(2)油性底涂液的配置； 油性溶剂 1份、粘结剂 B 0.03〜0.6份、粉体纳米导电 碳复合导电剂 0.03~0.6份。
所述的粘结剂 B为聚偏氟乙烯（PVDF),其分子量为 100-110万之间所述的 油性溶剂为 NMP, 溶剂纯度大于 98%。
所述的粉体纳米导电碳复合导电剂与粘结剂 B以 1 : 0.1-0.8的比例混合而 成。
所述的纳米导电碳复合导电剂是由纳米导电碳与 Spper P以 10: 1〜5的比 例复合而成， 纳米导电碳的直径为 10nm— 1000nm。
2)、 超声波分散：
( 1 ) 水性底涂液超声波分散； 将粘结剂 A和水性溶剂进行混合机械搅拌 1〜2 小时， 直至粘结剂 A完全与水性溶剂溶解形成粘结剂体系 A; 之后在超声波分 散条件下分三次每隔 30分钟在上述体系中加入粉体纳米导电碳复合导电剂， 并 机械搅拌 1〜2小时直至形成稳定的水性底涂液。
(2) 油性底涂液超声波分散； 将油性溶剂和粘结剂 B进行混合机械搅拌 5〜6 小时，直至粘结剂 B完全与油性溶剂溶解形成粘结剂体系 B;之后在超声波分散 条件下分三次每隔 30分钟在上述体系中加入粉体纳米导电碳复合导电剂， 并机 械搅拌 5〜6小时直至形成稳定的油性底涂液。
用上述二种配置的方法最后得到粘度为 200〜20000cps的底涂液。
一种铝箔预涂纳米导电碳底涂液的涂敷方法，其特征在于：是将上述经配置 好的水性或油性底涂液经过 lu过滤筛过筛后， 用凹版转移涂敷或用喷涂技术涂 敷在铝箔表面， 其厚度为（0.1〜10) μ πι, 干燥后在其表面上再涂敷上磷酸铁锂 正极材料， 并以人造石墨作为负极材料， 采用 LiPF6/EC+DEC、 体积比 1： 1为 电解液， Celgard 2400膜为隔膜， 制备出 5AH软包电池。 本发明， 其制备的电池内阻小、粘附力强、 导电性好、压实密度大， 尤其对 电池的大倍率放电具有明显的效果。并根据电池设计的要求，依据底涂液的粘度 涂敷出不同厚度的导电集流体， 提高了电池的不同性能。
附图说明
图 1是本发明的电池 A内阻曲线图。
图 2是电池 A的电压-放电容量倍率曲线图。
具体实施方式
实施例 1 :
铝箔预涂纳米导电碳水性底涂液的配置， 以质量百分比计。
称取 1000克二次蒸馏水水性溶剂和 200克水性粘结剂 A进行机械搅拌 2小 时， 得到均一、 稳定的粘结剂体系； 在超声波分散条件下分三次每隔 30分钟加 入 25克 (总质量为 75 克)粉体纳米导电碳复合导电剂，再用超声波超声分散 2小 时，最后得到粘度为 8000cps的水性底涂液。这里的纳米导电碳复合导电剂是 20 克纳米导电碳和 5克 Supper P复合导电剂混合而成。 选用纳米导电碳与 Spper P 复合不但可以增加底涂液的导电性， 同时可以提髙涂敷面的平整度。
实施例 2:
铝箔预涂纳米导电碳水性底涂液的配置， 以质量百分比计。
称取 1000克酒精水性溶剂和 200克水性粘结剂 A进行机械搅拌 1小时，得 到均一、 稳定的粘结剂体系； 在超声波分散条件下分三次每隔 30分钟加入 18 克 (总质量为 54克)粉体纳米导电碳复合导电剂， 再用超声波超声分散 2小时， 最后得到粘度为 2000cps的水性底涂液。 这里的纳米导电碳复合导电剂是 15克 纳米导电碳和 3克 Supper P复合导电剂混合而成。
水性溶剂为二次蒸馏水或浓度为 10%~80%的酒精 /IPA, 由于二次蒸馏水或 酒精、 IPA中含有羟基基团可以更好地与粘结剂中的羟基基团相容。
所述的水性粘结剂 A是浓度为 15%的丙烯酸与丙烯氰形成交联聚合物、 分 子量为 2000〜30000之间的粘结剂。选用丙烯酸与丙烯氰形成交联聚合物作为粘 结剂及其分子量可以使粘结剂与铝箔、粘结剂与磷酸铁锂活性物质之间有更好的 粘附力。
实施例 3: 铝箔预涂纳米导电碳油性底涂液的配置， 以质量百分比计。
称取 1000克纯度为大于 98%的 N-甲基吡咯垸酮 NMP作为油性溶剂、 35克 聚偏二氟乙烯 PVDF作为粘结剂 B， 在高速搅拌下机械搅拌 6小时， 得到均一、 稳定的粘结剂体系； 之后分三次每隔 30分钟加入 20克 (总质量为 60克)的粉体 纳米导电碳复合导电剂体系，并再采用超声波超声分散 2小时，最后加入质量为 300克 NMP调整粘度， 并最终得到粘度在 3000 cps的油性底涂液。 其中纳米导 电碳复合导电剂是由 10克纳米导电碳和 5克 Supper P复合导电剂混合而成。
选用粘结剂 B为聚偏氟乙烯（PVDF),其分子量为 100-110万之间所述的油 性溶剂为 NMP, 溶剂纯度大于 98%可以使粘结剂与铝箔、 粘结剂与磷酸铁锂活 性物质之间有更好的粘附力。
实施例 4:
铝箔预涂纳米导电碳油性底涂液的配置， 以质量百分比计。
称取 1000克纯度为大于 98%的 N甲基吡咯垸酮 NMP作为油性溶剂、 30克 聚偏二氟乙烯 PVDF作为粘结剂 B， 在高速搅拌下机械搅拌 5小时， 得到均一、 稳定的粘结剂体系； 之后分三次每隔 30分钟加入 66克 (总质量为 198克)粉体纳 米导电碳复合导电剂体系， 并再采用超声波超声分散 1 小时， 最后加入质量为 800克 NMP调整粘度， 并最终得到粘度在 2000 cps的油性底涂液。 其中纳米导 电碳复合导电剂是由 7克纳米导电碳和 4克 Supper P复合导电剂混合而成。
以上 1-4的实施例中纳米导电碳的粒径为 10nm— lOOOnm; 选用纳米导电碳 与 Spper P复合不但可以增加底涂液的导电性， 同时可以提高涂敷面的平整度。
选用上述粘结剂及其分子量可以使粘结剂与铝箔、粘结剂与磷酸铁锂活性物 质之间有更好的粘附力。
一种铝箔预涂纳米导电碳底涂液的涂敷方法， 是将上述实施例 1一 4中制得 的底涂液， 经过 lii过滤筛过筛后， 用凹版转移涂敷或用喷涂技术涂敷在铝箔表 面， 其厚度为 （0.1〜10) μ ιη, 干燥后在其表面上再涂敷上磷酸铁锂正极材料， 并以人造石墨作为负极材料，采用 LiPF6/EC+DEC、体积比 1： 1为电解液， Celgard 2400膜为隔膜， 制备出 5AH软包电池。
涂敷一定厚度的底涂液，目的是为增大磷酸铁锂活性物质与集流体的接触面 积， 太薄起不到增大接触面积的作用， 太厚会降低单体电池的体积能量， 影响电 池的整体性能。
对比试验： 未在铝箔表面涂敷本发明的底涂液的， 以铝箔为集流体， 其厚度 为 （0.1〜10 ) μ ιη, 磷酸铁锂为正极材料， 人造石墨作为负极材料， 采用 LiPFe/EC+DEC (体积比 1： 1 ) 为电解液， Celgard 2400膜为隔膜， 制备出 5AH 软包电池 B， 作为对比电池。
从图 1可以看出， 电池在每次放电 10%电量条件下测试其电池 A和电池 B 的直流内阻与放电容量百分比关系， 得出直流内阻 -放电容量百分比曲线图。 由 图中可以看出在集流体铝箔表面涂敷底涂层后， 直流内阻（平均值为 3 ιη Ω )得 到明显降低， 明显优于未涂敷电池的直流内阻 （平均值为 5 ηι Ω )， 同时电池的 直流内阻波动性也优于未涂电池的直流内阻。
从图 2可以看出， 电池 Α和电池 Β在倍率为 0.3C和 2C条件下测试其电压- 放电容量曲线图。可以看出涂敷后电池 A在 2C条件下容量保持率为 96%, 明显 优于未涂敷电池 B在倍率为 2C条件下的容量保持率 88%。

Claims

权利要求
1. 一种铝箔预涂纳米导电碳底涂液的配置， 以质量百分比计， 包括以下步 骤： 1 )配置底涂液 ； 2)超声波分散； 其特征在于：
1 )、 配置底涂液-
( 1 )水性底涂液的配置； 水性溶剂 1份、 粘结剂 A 0.05〜0.6份、 粉体纳米 导电碳复合导电剂 0.05~0.6份；
(2) 油性底涂液的配置； 油性溶剂 1份、 粘结剂 B 0.03〜0.6份、 粉体纳米 导电碳复合导电剂 0.03~0.6份；
2)、 超声波分散：
( 1 )水性底涂液超声波分散；将粘结剂 A和水性溶剂进行混合机械搅拌 1〜 2小时，直至粘结剂 A完全与水性溶剂溶解形成粘结剂体系 A; 之后在超声波分 散条件下分三次每隔 30分钟在上述体系中加入粉体纳米导电碳复合导电剂， 并 机械搅拌 1〜2小时直至形成稳定的水性底涂液；
(2)油性底涂液超声波分散； 将油性溶剂和粘结剂 B进行混合机械搅拌 5〜 6小时， 直至粘结剂 B完全与油性溶剂溶解形成粘结剂体系 B; 之后在超声波分 散条件下分三次每隔 30分钟在上述体系中加入粉体纳米导电碳复合导电剂， 并 机械搅拌 5~6小时直至形成稳定的油性底涂液。
2.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液（1 )工序中： 所述的粘结剂 A是丙烯酸与丙 烯氰形成交联聚合物， 其分子量为 2000〜30000之间。
3.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液（1 )工序中： 所述的水性溶剂为二次蒸馏水 或浓度为 10%~95%的酒精、 IPA。
4.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液（1 )工序中： 所述的粉体纳米导电碳复合导 电剂与粘结剂 A以 0.1〜0.6： 1的比例混合而成。
5.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液（1 )工序中： 所述的纳米导电碳复合导电剂 是由纳米导电碳与 Spper P以 10: 0.5〜6的比例复合而成， 所用纳米导电碳的粒 径为 lOnm— 1000nm。
6.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液 （2) 工序中： 所述的粘结剂 B为聚偏氟乙烯 PVDF,其分子量为 100-110万之间所述的油性溶剂为 NMP,溶剂纯度大于 98%。
7.根据权利要求 1所述的一种铝箔预涂纳米导电碳底涂液的配置， 其特征 在于： 所述的步骤 1 )配置底涂液（2)工序中： 所述的粉体纳米导电碳复合导 电剂与粘结剂 B以 1 : 0.1-0.8的比例混合而成。
8.一种根据权利要求 1所述制得的铝箔预涂纳米导电碳底涂液的涂敷方法， 其特征在于： 是将上述经配置好的水性或油性底涂液经过 1 μ m过滤筛过筛后， 用凹版转移涂敷或用喷涂技术涂敷在铝箔表面， 其厚度为（0.1〜10) u rn, 干燥 后在其表面上再涂敷上磷酸铁锂正极材料。
PCT/CN2011/001140 2011-06-08 2011-07-11 一种铝箔预涂纳米导电碳底涂液的配置及其涂敷的方法 Ceased WO2012167407A1 (zh)

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