WO2009115004A1 - 锂离子电池用水性粘合剂、制备方法及锂离子电池正极片 - Google Patents

锂离子电池用水性粘合剂、制备方法及锂离子电池正极片 Download PDF

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Publication number
WO2009115004A1
WO2009115004A1 PCT/CN2009/070464 CN2009070464W WO2009115004A1 WO 2009115004 A1 WO2009115004 A1 WO 2009115004A1 CN 2009070464 W CN2009070464 W CN 2009070464W WO 2009115004 A1 WO2009115004 A1 WO 2009115004A1
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Prior art keywords
lithium ion
ion battery
aqueous binder
aqueous
battery according
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PCT/CN2009/070464
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English (en)
French (fr)
Inventor
潘中来
邓正华
杜鸿昌
高建东
陈勉忠
邓佳闽
汪沣
李仁贵
王璐
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常州中科来方能源科技有限公司
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Priority to KR1020097020371A priority Critical patent/KR101119801B1/ko
Priority to JP2010503344A priority patent/JP5002052B2/ja
Publication of WO2009115004A1 publication Critical patent/WO2009115004A1/zh

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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 present invention relates to a binder for a lithium ion battery and a method for producing the same, and to a field of manufacturing an energy storage device such as a battery.
  • Lithium-ion batteries have advantages that are unmatched by other batteries: high energy density, long life, small size, and no pollution. They are widely used in electric vehicles, aerospace, communication equipment, and various portable appliances, and are ideal mobile power sources.
  • the lithium ion battery is mainly composed of a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte; the positive and negative electrodes are mixed and electropolished by an electroactive material, a conductive agent and a binder solution to form a slurry, which is coated as a current collector. On the copper foil and aluminum foil, it is processed by drying and rolling.
  • Lithium-ion battery electrode material adhesives mainly have two major categories, one is the most widely used fluoropolymer solvent-based adhesive; the other is water-based adhesive represented by LA132 and SBR.
  • SBR water-based adhesive uses water as a dispersion medium for powder materials. It is environmentally friendly and non-polluting, and is harmless to production operators. However, SBR water-based adhesives can only be used as binders for lithium ion battery anode materials due to the chemical nature of the material components.
  • LA132 water-based adhesive (ZL01108511.8, ZL01108524.X) can be used as a binder for positive and negative powder materials of lithium ion batteries.
  • the lithium ion battery fabricated by it has excellent electrical properties.
  • the use of it in the positive electrode has the following disadvantages: 1.
  • the compaction density of the positive electrode is low, that is, in the case of the same weight of the pole piece, the thickness of the pole piece is large, and the volumetric energy density of the lithium ion battery is lowered; After being brittle and soft, the pole piece is easily broken during the battery manufacturing process, reducing the yield of battery production. So far, there is no ideal aqueous binder for lithium ion battery cathode powder materials.
  • the object of the present invention is to prepare a novel low-cost, zero-pollution aqueous binder by a polymer modification method, overcome the defects of the above-mentioned binder for lithium ion battery positive electrodes, and improve the quality of the lithium ion battery.
  • the aqueous binder for lithium ion batteries of the present invention which comprises polyvinyl alcohol or an acetal derivative thereof as a host polymer, and two or more monomers having different polarities as graft comonomers in an aqueous medium
  • the aqueous polymer emulsion formed by the graft modification can be used as an electrode material binder.
  • the weight ratio of the host polymer to the graft comonomer is 30 to 95: 5 to 70, preferably 50 to 70: 50 to 30.
  • the adhesive is characterized by an emulsion form, a solid content of 5 to 40%, and a viscosity of 200 to 20,000 cps (40 ° C).
  • the host polymer is a water-soluble polyvinyl alcohol or an acetalized derivative thereof, and the polyvinyl alcohol (or an acetal derivative thereof) has a degree of polymerization of between 1700 and 2400 and a degree of hydrolysis of 50 to 99.
  • the graft comonomer of CH 2 CH 2 CH 2 CH 3 or -CN heap may also be a combination of at least one of the above olefins and an epoxy olefin.
  • the lithium ion battery electrode material of the present invention is aqueously bonded.
  • the preparation method is as follows: first, the polyvinyl alcohol or its acetal derivative is placed in a reaction vessel together with distilled water as a dispersion medium, and stirred while being heated until completely dissolved; and then part or all of the graft comonomer is added.
  • the solution of the reactor pass high-purity nitrogen to drive oxygen; adjust the temperature and keep the temperature constant to 30 ⁇ 90 °C; add initiator to initiate grafting, the remainder of the graft comonomer and the additional initiator during the reaction Adding dropwise or in portions, the polymerization time is 5 to 30 hours, and after the reaction is completed, the residual monomer is vacuum-extracted to obtain a lithium ion battery electrode material.
  • the water-based adhesive The lithium-ion battery positive electrode material aqueous binder of the invention has adhesive properties, electrochemical properties, etc., and the lithium ion battery electrode sheets are fabricated and assembled according to the lithium ion battery production process familiar to those skilled in the art.
  • the aluminum-plastic film flexible packaging battery was subjected to charge and discharge test.
  • the results showed that the compacted density of the positive electrode prepared by the aqueous binder of the lithium ion battery of the present invention was higher, and the volumetric energy density of the lithium ion battery was improved. Meanwhile, after the pole piece was dried, Good flexibility, which is good for battery production and improves the yield of battery production.
  • the aqueous binder for lithium ion batteries of the present invention is mainly composed of polyvinyl alcohol or an acetal derivative thereof, and two or more monomers having different polarities are used as graft comonomers.
  • An aqueous polymer emulsion formed by graft modification in an aqueous medium can be used as an electrode material binder.
  • the method for preparing an aqueous binder for a lithium ion battery electrode of the present invention comprises: first placing polyvinyl alcohol and an acetal derivative thereof in a reaction vessel together with distilled water as a dispersion medium, and heating and dissolving while stirring and mixing. a stirring rate of 20 ⁇ 700 rpm / min, a temperature of 60 ⁇ 90 ° C; then the portion of the monomer or graft copolymerization all added to the reactor solution, high pure nitrogen purge oxygen 0.
  • the weight ratio of the host polymer to the graft comonomer is 30 to 95: 5 to 70, preferably 50 to 70: 50 to 30.
  • the host polymer is a water-soluble polyvinyl alcohol or an acetalized derivative thereof, and the polyvinyl alcohol (or an acetal derivative thereof) has a degree of polymerization of between 1700 and 2400 and a degree of hydrolysis of 50 to 99.
  • the graft comonomer is an olefin of two or more different polarities of the formula CHR ⁇ CR, wherein
  • R 1 -H -CH 3 or - COOLi
  • R 2 -H, -CH 3 or - COOLi
  • R 3 -COOLi, -CO H 2 , -CO HCH 3 , -C 6 H 5 , -OCOCH 3 , -COOCH 2 CH 2 CH 2 CH 3 , -COOCH 2 CH (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 or -CN.
  • the graft comonomer may also be a combination of at least one of the above olefins and an epoxy olefin.
  • the initiator system used in the reaction may be a water-soluble initiator such as ammonium persulfate, potassium persulfate, hydrogen peroxide or azobisisobutyronitrile, or these initiators may be combined with NaHS0 3 , ?
  • a redox initiation system consisting of ⁇ 0 4 and the like. 5 ⁇ 1. 5% ⁇ The amount of the initiator is 0. 5 ⁇ 1. 5%.
  • the solid content of the aqueous binder of the positive electrode material for lithium ion battery obtained by the above preparation method is in the range of 5 to 40%
  • the positive electrode materials to which the aqueous binder for lithium ion batteries is applied in the present invention are LiFeP0 4 , LiCo0 2 , LiNi0 2 , LiMn 2 0 4 and a mixture thereof. In the fabricated electrode sheet, the content of the aqueous binder is 2 to 8%, and 4 to 6%. It is better.
  • the lithium ion battery positive electrode sheet is prepared by using the lithium ion battery production process of the lithium ion battery of the present invention, and is assembled into an aluminum plastic film flexible packaging battery for charging and discharging test. The production process is as follows: 1.
  • the positive electrode of the lithium ion battery of the present invention is diluted with a binder to a concentration of 5%, and 60 parts of the diluted binder is weighed and added to 90 parts of LiCo0 2 or 1 ⁇ 3 ⁇ 41 0 4 positive electrode powder material, and 7 parts of conductive material.
  • the additive is mixed and ground into a slurry, uniformly coated on a clean aluminum foil, and dried and compacted to obtain a LiCo0 2 or LiM 0 4 positive electrode sheet;
  • EC diethyl carbonate
  • EMC ethyl methyl carbonate
  • battery test is based on lithium-ion battery charge familiar to those skilled in the art The discharge conditions are carried out.
  • the following non-limiting examples are intended to provide a further understanding of the invention, and the scope of the invention is not limited by the scope of the invention.
  • Example 1 Preparation of an aqueous binder for a positive electrode of a lithium ion battery
  • propylene oxide (AM0), acrylamide (AM) and vinyl acetate (VAc) were combined with polyvinyl alcohol (PVA) in an aqueous phase.
  • PVA polyvinyl alcohol
  • the above aqueous binder for a lithium ion secondary battery is prepared by adding 60 parts of polyvinyl alcohol (degree of polymerization: 1700, degree of hydrolysis 99%) and 400 parts of distilled water to the reaction vessel, and heating to 95°. C, stirring and dissolving, rotating at 300 rpm; after complete dissolution, cooling and constant temperature at 50 ° C; introducing nitrogen to oxygen for 2 hours, adding 10 parts of propylene oxide, 10 parts of acrylamide and 20 parts of vinyl acetate, then 5 parts of ammonium persulfate and 0.4 parts of sodium sulfite were added, and the reaction was completed after 12 hours.
  • a lithium ion battery positive electrode aqueous binder having the above composition was obtained.
  • Example 2 Preparation of aqueous binder for lithium ion battery positive electrode
  • the preparation and operating conditions of the adhesive of this example were basically the same as those of Example 1, except that propylene oxide (P0X) was replaced by acrylonitrile (AN).
  • P0X propylene oxide
  • AN acrylonitrile
  • 60 parts of polyvinyl alcohol and 400 parts of distilled water were added to the reaction vessel, and after completely dissolved, the temperature was kept at 50 ° C; 15 parts of acrylamide, 10 parts of acrylonitrile and 15 parts of vinyl acetate were added, and the reaction was completed after 20 hours.
  • Example 3 Preparation of an aqueous binder for a positive electrode of a lithium ion battery
  • BA butyl acrylate
  • Example 4 Preparation of an aqueous binder for a positive electrode of a lithium ion battery
  • EHA isopropyl acrylate
  • Example 5 Preparation of Lithium Ion Battery Positive Electrode Adhesive Example
  • the following is a practical application of the aqueous binder of the present invention in a lithium ion battery.
  • Example 6 The performance parameters of the positive electrode tab prepared by using the aqueous binder of the present invention are LiCo0 2 and LiM 0 4 as positive electrode materials, and Examples 1 to 3 are obtained.
  • the emulsion is a binder, and a conductive agent is used to prepare a positive electrode sheet having a composition of 90% positive electrode material, 7% conductive agent, and 3% binder; matching positive and negative electrode sheets, assembling into a lithium ion battery for constant current charge and discharge Test; battery separator is Cellgard-2400, electrolyte is 1.0M LiPF 6 /EC+DEC+EMC (l : 1 : 1), and the electrode pieces of the emulsions of Examples 1 to 3 as adhesives are shown in Table 1.
  • the battery cycle and discharge curves are shown in Table 2 and Figure 1. Table 1. LiCo0 2 and LiMn 2 0 4 positive pole parameters
  • the results of Table 1 and Table 2 show that the positive electrode prepared by using the aqueous binder of the positive electrode of the lithium ion battery of the present invention has higher compaction density than the positive electrode piece using LA132 as a binder, and can significantly improve the lithium ion battery. Volumetric energy density.
  • the pole piece is soft and good, which is very advantageous in the battery manufacturing process, which greatly improves the yield of battery production.
  • the battery has excellent charge and discharge cycle capacity performance.
  • the method of modifying the polymer of the present invention provides an ideal binder for lithium ion batteries.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

锂离子电池用水性粘合剂、 制备方法及锂离子电池正极片 技术领域 本发明涉及锂离子电池用粘合剂及其制造方法， 属于电池等储能器件制造领域。 背景技术 锂离子电池具有其它电池不可比拟的优点： 能量密度高、 寿命长、 体积小、 无污 染， 广泛用于电动车辆、 航天航空、 通讯设备以及各类便携式电器， 是最理想的移动 电源。 锂离子电池主要由正电极、 负电极、 隔膜和非水电解液等组成； 正、 负电极由电 活性材料、 导电剂与粘合剂溶液混合研磨均匀成为浆料， 涂布于作为集电体的铜箔、 铝箔上， 经干燥、 碾压等工艺处理而成。 锂离子电池电极材料粘合剂主要有两大类， 一是目前应用最多的含氟聚合物溶剂型粘合剂； 二是以 LA132、 SBR为代表的水性粘 合剂。
以含氟烯烃聚合物溶液为锂离子电池正负极电极材料的粘合剂， 有两个明显的缺 点： 1. 在电极制作过程溶剂的挥发， 易对环境产生污染， 并对操作人员的健康有较大 的危害； 2. 大大增加了锂离子电池的生产成本， 溶剂必需用特殊的冷冻设备收集并加 以处理， 含氟聚合物及其溶剂价格昂贵。
SBR水性粘合剂以水为粉体材料的分散介质， 它对环境友好、 无污染， 对生产操 作人员无危害。 但 SBR水性粘合剂由于材料组份的化学特性的限制， 它只能作为锂离 子电池负极粉体材料的粘合剂。
LA132水性粘合剂 (ZL01108511.8， ZL01108524.X)可作为锂离子电池正负极粉体 材料的粘合剂， 用它制作的锂离子电池具有优良的电性能。 但在正极中使用它存在如 下缺点： 1.正极压实密度偏低， 即在极片重量相同的情况下， 极片厚度较大， 降低了锂 离子电池的体积能量密度； 2.极片干燥后较脆、 柔软性差， 在电池制作过程中极片容易 折断， 降低电池生产的成品率。 到目前为止， 尚没有一种较理想的用于锂离子电池正极粉体材料的水性粘合剂。 发明内容 本发明的目的在于： 用聚合物改性的方法， 制备新型的低成本、 零污染的水性粘 合剂， 克服上述锂离子电池正极用粘合剂的缺陷， 提高锂离子电池的质量。 本发明的锂离子电池用水性粘合剂， 以聚乙烯醇或其缩醛衍生物为主体聚合物， 以两种或两种以上不同极性的单体作为接枝共聚单体， 在水介质中接枝改性后形成的 水性聚合物乳液， 即可作为电极材料粘合剂。 其中，主体聚合物和接枝共聚单体的重量比为 30〜95： 5〜70，优选 50〜70： 50〜 30。 粘合剂外观特征为乳液状， 固含量 5〜40%， 粘度为 200〜20000厘泊 （40°C )。 所述的主体聚合物为水溶性的聚乙烯醇或其缩醛化衍生物， 聚乙烯醇 （或其缩醛 衍生物） 聚合度为 1700〜2400之间， 水解度 50〜99。 所述的接枝共聚单体是结构式为 CHR^CI^R3的两种或两种以上不同极性的烯烃， 其中， Ι^=-Η或 -CH3 ; R2=-H、 -CH3或- COOLi; R3=-COOLi、 -CO H2、 -CO HCH3、 -C6H5、 -OCOCH3、 -COOCH2CH2CH2CH3、 -COOCH2CH (CH2CH3) CH2CH2CH2CH3或 -CN„ 所述的接枝共聚单体还可以是上述烯烃中的至少一种与环氧基烷烃的组合。 本发明的锂离子电池电极材料水性粘合剂的制备方法是： 先将聚乙烯醇或其缩醛 衍生物与作为分散介质的蒸馏水一起置于反应容器中， 边加热边搅拌至完全溶解； 再 将接枝共聚单体的部分或全部加入反应器的溶液中， 通入高纯氮气驱氧； 调节温度并 恒温至 30〜90°C ; 加引发剂引发接枝， 接枝共聚单体的剩余部分和补加的引发剂在反 应过程中滴加或分次加入， 聚合反应时间为 5〜30 小时， 反应结束后真空抽除残余单 体， 便得到锂离子电池电极材料水性粘合剂。 本发明的锂离子电池正极材料水性粘合剂， 其粘合性能、 电化学性能等， 按本行 业技术人员均熟悉的锂离子电池生产工艺制作锂离子电池电极片并组装成铝塑膜软包 装电池进行充放电测试考察， 结果显示， 由本发明的锂离子电池用水性粘合剂制备的 正极压实密度较高， 提高了锂离子电池的体积能量密度； 同时， 极片干燥后柔软性良 好， 利于电池制作， 提高了电池生产的成品率。 具体实施方式 本发明的锂离子电池用水性粘合剂以聚乙烯醇或其缩醛衍生物为主体聚合物， 以 两种或两种以上不同极性的单体作为接枝共聚单体， 在水介质中接枝改性后形成的水 性聚合物乳液， 即可作为电极材料粘合剂。 本发明的锂离子电池电极用水性粘合剂的制备方法是： 先将聚乙烯醇及其缩醛衍 生物与作为分散介质的蒸熘水一起置于反应容器中， 边搅拌混合边加热至溶解， 搅拌 速度为 20〜700转 /分， 温度为 60〜90°C ; 再将接枝共聚单体的部分或全部加入反应器 的溶液中， 通入高纯氮气驱氧 0. 5〜2小时； 调节恒温至 30〜90°C， 以 40〜60°C为佳； 加引发剂引发接枝， 接枝共聚单体的剩余部分和补加的引发剂在反应过程中滴加或分 次加入， 聚合反应时间为 5〜30小时， 以 15〜20小时为佳。 反应结束后真空抽除残余 单体， 便得到锂离子电池电极材料水性粘合剂。 其中， 主体聚合物和接枝共聚单体的 重量比为 30〜95： 5〜70， 以 50〜70： 50〜30为佳。 所述的主体聚合物为水溶性的聚乙烯醇或其缩醛化衍生物， 聚乙烯醇 （或其缩醛 衍生物） 聚合度为 1700〜2400之间， 水解度 50〜99。
所述的接枝共聚单体是结构式为 CHR^CR 的两种或两种以上不同极性的烯烃， 其 中，
R1=-H -CH3或 - COOLi;
R2=-H、 -CH3或 - COOLi;
R3=-COOLi、 -CO H2、 -CO HCH3、 -C6H5、 -OCOCH3、 -COOCH2CH2CH2CH3、 -COOCH2CH (CH2CH3) CH2CH2CH2CH3或 -CN。 所述的接枝共聚单体还可以是上述烯烃中的至少一种与环氧基烷烃的组合。 反应中采用的引发体系可以为过硫酸铵、 过硫酸钾、 过氧化氢、 偶氮二异丁腈等 水溶性引发剂， 也可以是这些引发剂与 NaHS03、 ？^04等构成的氧化还原引发体系。 引 发剂用量则占单体总重量的 0. 5〜1. 5%。 用上述制备方法所得到的锂离子电池正极材料水性粘合剂的固含量范围 5〜40%
(重量百分数， 下同）， 并以 10〜20%为佳； 粘度为 200〜20000厘泊 （40°C )。 本发明中锂离子电池用水性粘合剂所适用的正极材料为 LiFeP04、 LiCo02、 LiNi02、 LiMn204及其多元混合物等。 在制造的电极片中， 水性粘合剂的含量为 2〜8%， 以 4〜6% 为佳。 采用本发明的锂离子电池用水性粘合剂按本行业技术人员均熟悉的锂离子电池生 产工艺制作锂离子电池正极片并组装成铝塑膜软包装电池进行充放电测试考察， 其制 作过程如下： 1.将本发明的锂离子电池正极用粘合剂稀释至浓度为 5%， 称取该稀释后粘合剂 60 份加入 90份 LiCo02或 1^¾1 04正极粉体材料、 7份导电添加剂混合研磨成浆料， 均匀涂 布在洁净的铝箔上， 烘干压实后， 得到 LiCo02或 LiM 04正极电极片；
2.将商品 LA132水性粘合剂稀释至浓度为 5%，称取该粘合剂 100份加入 95份碳素 负极材料混合， 充分研磨成浆料， 均匀涂布在洁净的铜箔上， 烘干后碾压密实， 即得 到负极电极片；
3. 将制作好的锂离子电池正负极片按电池容量规格尺寸裁成一定面积的电极片， 以 Cellgard-2400作为电池隔膜， 制作 LiMn204/石墨或 LiCo02/石墨卷绕式锂离子电池， 以铝塑膜封装， 在 80 ± 10°C的温度下真空干燥 10〜48小时后， 转移到干燥氩气氛的手 套箱中， 注入电解液， 电解液为 LiPF6/碳酸乙烯酯 (EC) +碳酸二乙酯 (DEC) +碳酸甲乙酯 (EMC) , EC: DEC: EMC=1 : 1 : 1 (重量比）； 电池测试均按本行业技术人员均熟悉的锂离子 电池充放电条件进行。 以下非限定性实施例更具体详细的描述， 将有助于本发明的理解， 本发明的保护 范围不受这些实施例的限定， 本发明的保护范围由权利要求来决定。 实施例 1 锂离子电池正极用水性粘合剂的制备 本实施例中以环氧丙烷 （Ρ0Χ)、 丙烯酰胺 （AM) 和醋酸乙烯酯 （VAc) 在水相中与 聚乙烯醇 （PVA) 接枝共聚， 制备出用于锂离子电池正极片的水性粘合剂， 其组成为 P0X:AM: VAc : PVA=10 : 10 : 20 : 60 (重量比， 下同）， 乳液固含量为 20%， 产物为浅白色乳 液。 上述用于锂离子二次电池的水性粘合剂的制法是： 在反应容器中加入 60份聚乙烯 醇（聚合度为 1700， 水解度 99%)和 400份蒸熘水， 加热至 95°C， 搅拌溶解， 转速 300 转 /分； 完全溶解后降温并恒温于 50°C ; 通入氮气驱氧 2 小时， 加入 10份环氧丙垸、 10份丙烯酰胺和 20份醋酸乙烯酯， 然后加过硫酸铵 0. 7份、 亚硫酸钠 0. 4份， 反应 12小时后结束。 制得上述成分的锂离子电池正极水性粘合剂。 实施例 2 锂离子电池正极用水性粘合剂的制备 本实施例粘合剂的制法和操作条件与实施例 1 基本相同， 唯不同的是环氧丙烷 (P0X) 换为丙烯腈 （AN)， 在反应容器中加入 60份聚乙烯醇和 400份蒸熘水， 完全溶 解后恒温于 50°C; 加入 15份丙烯酰胺、 10份丙烯腈和 15份醋酸乙烯酯， 反应 20小 时后结束。 粘合剂的组成为 AM:AN:VAc:PVA=15:10:15:60， 乳液固含量为 20%， 为微黄 白乳液。 实施例 3锂离子电池正极用水性粘合剂的制备 本实施例粘合剂的制法同于实例 2， 唯一不同的是， 丙烯腈换为丙烯酸丁酯（BA)， 于温度 50°C反应 20小时； 粘合剂的组成为 AM:BA:VAc:PVA=15:10:15:60， 乳液固含量 为 20%， 为微黄白乳液。 实施例 4锂离子电池正极用水性粘合剂的制备 本实施例粘合剂的制法与实施例 2 基本相同， 唯不同是， 丙烯腈换为丙烯酸异辛 酉旨 (EHA); 于温度 50°C反应 30小时； 粘合剂的组成为 AM:EHA:VAc:PVA=15:10:15:60， 乳液固含量为 10%， 为白色乳液。 实施例 5锂离子电池正极用水性粘合剂的制备 实施例粘合剂的制法与实施例 2 基本相同， 唯不同是， 主体聚合物为聚乙烯醇缩 丁醛（PVB);于温度 50°C反应 30小时；粘合剂的组成为 AM: AN:VAc:PVB=15: 10: 15:60, 乳液固含量为 10%， 为白色乳液。 以下是本发明水性粘合剂在锂离子电池中的实际应用 实施例 6 采用本发明水性粘合剂制备的正极极片性能参数 以 LiCo02和 LiM 04为正极材料， 实施例 1〜3得到的乳液为粘合剂， 配合导电剂， 制得组成为 90%正极材料， 7%导电剂， 3%粘合剂的正极片； 匹配正、 负极片， 组装成锂 离子电池进行恒流充放电试验； 电池隔膜为 Cellgard-2400， 电解液为 1.0M LiPF6/EC+DEC+EMC(l : 1 : 1)， 实施例 1〜3的乳液作为粘合剂的极片参数如表 1所示， 其电池循环性和放电曲线如表 2和图 1所示。 表 1. LiCo02和 LiMn204正极极片参数
Figure imgf000008_0001
表 2. 各类实验电池的充放电循环容量
Figure imgf000008_0002
表 1和表 2结果显示， 采用本发明锂离子电池正极用水性粘合剂， 制备的正极与 采用 LA132为粘合剂的正极极片相比， 压实密度较高， 能显著提高锂离子电池的体积 能量密度。 另外， 极片柔软性良好， 这电池制作过程中非常有利， 极大地提高了电池 生产的成品率。 且电池的充放电循环容量性能优良。 本发明用聚合物改性的方法， 为 锂离子电池提供了一种理想的粘合剂。

Claims

权利要求书
1、 锂离子电池用水性粘合剂， 其特征在于： 它是以聚乙烯醇或其缩醛衍生物为主 体聚合物， 以两种或两种以上不同极性的单体作为接枝共聚单体， 在水介质中接枝改 性后形成的水性聚合物乳液， 乳液固含量 5〜40%， 粘度 200〜20000厘泊 （40°C )。
2、 根据权利要求 1所述的锂离子电池用水性粘合剂， 其特征在于： 所述的主体聚 合物聚乙烯醇或其缩醛化衍生物的聚合度为 1700〜2400之间， 水解度 50〜99。
3、 根据权利要求 1所述的锂离子电池用水性粘合剂， 其特征在于： 所述的接枝共 聚单体是： 结构式为 CHR^CI^R3的不同极性的烯烃中的至少两种，其中， Ι^=-Η、- CH3 ; R2=-H、 -CH3或 - COOLi； R3=-COOLi、 -CO H2、 -CO HCH3、 -C6H5、 -OCOCH3、 -COOCH2CH2CH2CH3、 -COOCH2CH ( CH2CH3 ) CH2CH2CH2CH3或 -CN; 或上述烯烃中的至少一种与环氧基烷烃的组合。
4、 制备权利要求 1-3任一项所述的锂离子电池用水性粘合剂的方法， 其特征在于 包括以下步骤： ( 1 ) 按主体聚合物和接枝共聚单体的重量比为 30〜95： 5〜70称取原料；
( 2) 将主体聚合物与蒸熘水一起置于反应容器中， 边加热边搅拌至完全溶解， 温 度为 60〜90°C ;
( 3) 将接枝共聚单体全部加入反应器的溶液中， 通入高纯氮气驱氧 0. 5〜2小时， 调节并恒温至 30〜90°C ; (4) 加引发剂引发接枝共聚， 聚合反应时间为 5〜30小时， 反应结束后真空抽除 残余单体， 得到锂离子电池用水性粘合剂。
5、 根据权利要求 4所述的制备锂离子电池用水性粘合剂的方法， 其特征在于： 聚 合反应是分步进行的， 第 （3 ) 步只加入一部分接枝共聚单体， 剩余部分在第 （4) 步 聚合反应过程中滴加或分次， 同时补加引发剂。
6、根据权利要求 4或 5所述的制备锂离子电池用水性粘合剂的方法，其特征在于: 反应中采用的引发体系为过硫酸铵、 过硫酸钾、 过氧化氢、 偶氮二异丁腈等水溶性引 发剂， 或前述引发剂与 NaHS03、 FeS04等构成的氧化还原引发体系； 引发剂用量占单 体总重量的 0.5〜1.5%。
7、根据权利要求 4或 5所述的制备锂离子电池用水性粘合剂的方法，其特征在于: 聚合反应温度为 40〜60°C， 时间 15〜20小时。
8、根据权利要求 4或 5所述的制备锂离子电池用水性粘合剂的方法，其特征在于: 控制乳液固含量为 10〜20%， 粘度为 200〜20000厘泊 （40°C )。
9、 锂离子电池正极极片， 其特征在于： 它是由权利要求 1-3任一项所述的锂离子 电池用水性粘合剂与锂离子电池正极粉体材料和导电剂制备而成， 其中水性粘合剂的 含量为 2〜8%。
10、 根据权利要求 9 所述锂离子电池正极极片， 其特征在于： 水性粘合剂的含量 为 4〜6%。
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