JP5002052B2 - Aqueous adhesive for lithium ion battery, method for producing the same, and lithium ion battery positive electrode sheet - Google Patents

Aqueous adhesive for lithium ion battery, method for producing the same, and lithium ion battery positive electrode sheet Download PDF

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JP5002052B2
JP5002052B2 JP2010503344A JP2010503344A JP5002052B2 JP 5002052 B2 JP5002052 B2 JP 5002052B2 JP 2010503344 A JP2010503344 A JP 2010503344A JP 2010503344 A JP2010503344 A JP 2010503344A JP 5002052 B2 JP5002052 B2 JP 5002052B2
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パン，ゾンライ
デン，ツェングア
ドゥ，ホンチャン
ガオ，ジャンドン
チェン，ミャンゾン
デン，ジャミン
ワン，フェン
リー，レンギ
ワン，ルー
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チャンゾウ ゾンケ ライファン パワー ディベロプメント カンパニー リミテッド
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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

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  • 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

本発明は、リチウムイオン電池用接着剤およびその製造方法に関し、電池などのエネルギー蓄積用機器を製造する分野に関する   The present invention relates to an adhesive for a lithium ion battery and a method for manufacturing the same, and to a field for manufacturing an energy storage device such as a battery.

リチウムイオン電池は、他の電池に比類なき長所を有し、高エネルギー密度、長寿命、小型、無汚染であり、電動車両、航空宇宙、通信機器および各種の携帯式電気製品に広く使用され、最も理想的な移動電源である。   Lithium ion batteries have unrivaled advantages over other batteries, high energy density, long life, small size, no pollution, widely used in electric vehicles, aerospace, communication equipment and various portable electrical products, It is the most ideal mobile power source.

リチウムイオン電池は、主に正極、負極、隔膜および非水電解液などから構成されている。正極および負極は、電気活性材料と、導電剤と、接着剤溶液とを混合し、均一に研磨してぺーストが得られ、コレクターとしての銅箔やアルミウム箔に塗布し、乾燥および研磨などのプロセスを経て得られる。リチウムイオン電池の電極材料の接着剤は主に二種類があり、一種目は現在最もよく使用されているフッ素を含有するポリマーの溶媒型接着剤であり、二種目はLA132、SBRを代表とする水性接着剤である。   A lithium ion battery is mainly composed of a positive electrode, a negative electrode, a diaphragm, a non-aqueous electrolyte, and the like. A positive electrode and a negative electrode are mixed with an electroactive material, a conductive agent, and an adhesive solution, and are uniformly polished to obtain a paste, which is applied to a copper foil or aluminum foil as a collector, dried, polished, etc. Obtained through a process. There are mainly two types of adhesives for electrode materials of lithium ion batteries. The first type is the most commonly used solvent-based adhesive for fluorine-containing polymers, and the second type is represented by LA132 and SBR. It is a water-based adhesive.

フッ素を含有するアルケンポリマー溶剤液をリチウムイオン電池正負極用電極材料の接着剤とすることには、二つの明らかな欠点がある。即ち、１．電極を製造する過程で溶媒が蒸発し、環境を汚染しやすく、且つ作業員の健康を大きく害する。２．溶媒を特殊な冷凍設備で収集して処理する必要があり、フッ素を含有するポリマーおよびその溶媒の価格がとても高く、リチウムイオン電池の製造コストを大幅に増加させる。   There are two obvious drawbacks to using an alkene polymer solvent solution containing fluorine as an adhesive for the electrode material for the positive and negative electrodes of a lithium ion battery. That is: In the process of manufacturing the electrode, the solvent evaporates, which easily contaminates the environment and greatly harms the health of workers. 2. Solvents need to be collected and processed in special refrigeration equipment, and the price of fluorine-containing polymers and their solvents is very high, greatly increasing the cost of manufacturing lithium ion batteries.

SBR水性接着剤は水を粉末材料の分散媒質として、環境に優しく、汚染がなく、作業員に害を与えない。但し、SBR水性接着剤は材料組成分の化学的特性の制限により、リチウムイオン電池の負極粉末材料の接着剤のみとして使用される。   SBR water-based adhesives use water as a dispersion medium for powder materials, are environmentally friendly, are free from pollution, and do not harm workers. However, the SBR aqueous adhesive is used only as an adhesive for the negative electrode powder material of the lithium ion battery due to the limitation of the chemical properties of the material composition.

LA132水性接着剤（中国特許番号ZL01108511.8、ZL01108524.X）はリチウムイオン電池正負極の粉末材料の接着剤として使用でき、その接着剤で作られたリチウムイオン電池は優良な電気的性能を有する。但し、正極に使用されるのは以下の欠点を有する。即ち、１．正極の圧密度が低く、即ち、極シート重量が同じである場合、極シートの厚みが大きくなり、リチウムイオン電池の体積エネルギー密度を低下させる。２．極シートが乾燥した後に脆くなり、柔軟性が悪くなり、電池を製造する過程中では極シートが折れやすく、電池製造の歩留まりが低下される。   LA132 water-based adhesive (Chinese patent numbers ZL01108511.8, ZL01108524.X) can be used as an adhesive for the powder material of lithium ion battery positive and negative electrodes, and the lithium ion battery made with the adhesive has excellent electrical performance . However, what is used for a positive electrode has the following faults. That is: When the pressure density of the positive electrode is low, that is, when the weight of the electrode sheet is the same, the thickness of the electrode sheet increases and the volume energy density of the lithium ion battery decreases. 2. The electrode sheet becomes brittle after being dried, the flexibility becomes poor, and the electrode sheet is easily broken during the process of manufacturing the battery, so that the yield of battery manufacturing is reduced.

いままでのところ、まだ比較的に理想的なリチウムイオン電池正極の粉末材料のための水性接着剤はない。   So far, there is still no water based adhesive for the powder material of the relatively ideal lithium ion battery positive electrode.

本発明は、ポリマー改質の方法を用いて、新型でコストが低く、無汚染の水性接着剤を製造し、上記リチウムイオン電池正極用接着剤の欠陥を克服し、リチウムイオン電池の品質を向上することを目的とする。   The present invention uses a polymer modification method to produce a new, low-cost, pollution-free water-based adhesive, overcoming the defects of the lithium-ion battery positive electrode adhesive and improving the quality of the lithium-ion battery. The purpose is to do.

本発明に係るリチウムイオン電池用水性接着剤は、ポリビニルアルコールまたはそのアセタール誘導体をベースポリマーとし、二種以上の異なる極性のモノマーをグラフト共重合モノマーとして、水媒質中でグラフト改質したことにより水性ポリマーラテックスが形成され、即ちそのポリマーラテックスを電極材料の接着剤とすることができる。   The aqueous adhesive for lithium ion batteries according to the present invention is water-based by graft modification in an aqueous medium using polyvinyl alcohol or an acetal derivative thereof as a base polymer and two or more different polar monomers as graft copolymerization monomers. A polymer latex is formed, that is, the polymer latex can be an adhesive for the electrode material.

その際、ベースポリマーとグラフト共重合モノマーとの重量比（ベースポリマー／グラフトモノマー）は30〜95：5〜70（即ち、３０／７０〜９５／５）であり、好ましくは50〜70：50〜30（即ち、５０／５０〜７０／３０）である。接着剤の外観特徴はラテックス状であり、固形物の含有量は5〜40重量％であり、粘度は200〜20000センチポアズ（cP）（40℃で測定時）である。   At that time, the weight ratio of the base polymer to the graft copolymerization monomer (base polymer / graft monomer) is 30 to 95: 5 to 70 (that is, 30/70 to 95/5), preferably 50 to 70:50. ˜30 (ie 50/50 to 70/30). The appearance characteristic of the adhesive is latex, the solid content is 5 to 40% by weight, and the viscosity is 200 to 20000 centipoise (cP) (when measured at 40 ° C.).

前記ベースポリマーは水溶性ポリビニルアルコールまたはそのアセタール誘導体であり、ポリビニルアルコール（またはそのアセタール誘導体）の重合度は1700〜2400の間、加水分解度は50〜99の間である。   The base polymer is water-soluble polyvinyl alcohol or its acetal derivative, and the degree of polymerization of polyvinyl alcohol (or its acetal derivative) is between 1700 and 2400, and the degree of hydrolysis is between 50 and 99.

前記グラフト共重合モノマーは、構造式がCHR1=CR2R3である二種以上の異なる極性のアルケンであり、その中、R１=-Hまたは-CH３である。R2=-H、-CH3または-COOLiである。R3=-COOLi、-CONH2、-CONHCH3、-C6H5、-OCOCH3、-COOCH２CH２CH２CH3、-COOCH2CH(CH2CH3)CH２CH2CH2CH3または-CNである。 The graft copolymerization monomer is an alkene having two or more different polarities whose structural formula is CHR 1 = CR 2 R 3 , in which R 1 = —H or —CH 3 . R 2 = -H, -CH 3 or -COOLi. R 3 = -COOLi, -CONH 2 , -CONHCH 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.

前記グラフト共重合モノマーは、上記アルケン中の少なくとも一種とエポキシアルカンとの組み合わせでもよい。   The graft copolymerization monomer may be a combination of at least one of the alkenes and an epoxy alkane.

本発明に係るリチウムイオン電池用電極材料の水性接着剤の製造方法は以下の通りである。即ち、まずポリビニルアルコールまたはそのアセタール誘導体と、分散媒質としての蒸留水とを反応容器中に入れ、完全に溶解するまで加熱しながら攪拌する。更にグラフト共重合モノマーの一部分または全部を反応器の溶液中に加え、高純度の窒素ガスを通して酸素を排除する。温度を30〜90℃まで調節して一定に保つ。開始剤を加えグラフト共重合を開始させ、反応過程中ではグラフト共重合モノマーの残余の部分および追加の開始剤を滴下し、または数回で加え、重合反応時間は5〜30時間であり、反応が終了した後、真空により残余のモノマーを取り除くことで、リチウムイオン電池用電極材料の水性接着剤が得られる。   The manufacturing method of the aqueous adhesive of the electrode material for lithium ion batteries which concerns on this invention is as follows. That is, first, polyvinyl alcohol or an acetal derivative thereof and distilled water as a dispersion medium are placed in a reaction vessel and stirred while heating until completely dissolved. Further, some or all of the graft copolymerization monomer is added to the reactor solution and oxygen is purged through high purity nitrogen gas. Adjust the temperature to 30-90 ° C and keep it constant. Initiator is added to initiate graft copolymerization, during the course of the reaction, the remaining part of the graft copolymerization monomer and additional initiator are added dropwise, or added several times, the polymerization reaction time is 5-30 hours, the reaction After the process is completed, the remaining monomer is removed by vacuum to obtain an aqueous adhesive for an electrode material for a lithium ion battery.

本発明に係るリチウムイオン電池用正極材料の水性接着剤の接着性能、電気化学的性能などについては、本分野の技術者が熟知するリチウムイオン電池製造プロセスに基づきリチウムイオン電池電極シートを製造し、且つアルミニウムプラスチック複合フィルムのフレキシブルパッケージの電池を組み立て、充放電を行い、測定結果を考察した。その結果、本発明に係るリチウムイオン電池用水性接着剤から製造された正極の圧密度が高く、リチウムイオン電池の体積エネルギー密度を向上すると同時に、極シートが乾燥した後でも柔軟性がよく、電池製造に有利であり、電池製造の歩留まりを向上させるものであった。   For the adhesive performance of the aqueous adhesive of the positive electrode material for lithium ion batteries according to the present invention, electrochemical performance, etc., a lithium ion battery electrode sheet is manufactured based on a lithium ion battery manufacturing process familiar to engineers in the field, And the battery of the aluminum plastic composite film flexible package was assembled, charged / discharged, and the measurement result was considered. As a result, the positive electrode manufactured from the water-based adhesive for lithium ion batteries according to the present invention has a high pressure density, improves the volume energy density of the lithium ion battery, and at the same time has good flexibility even after the electrode sheet is dried. This is advantageous for manufacturing and improves the yield of battery manufacturing.

本発明に係るリチウムイオン電池用水性接着剤は、ポリビニルアルコールまたはそのアセタール誘導体をベースポリマーとし、二種以上の異なる極性のモノマーをグラフト共重合モノマーとして、水媒質中でグラフト改質したことにより水性ポリマーラテックスが形成され、即ち、その水性ポリマーラテックスを電極材料の接着剤とすることができる。   The aqueous adhesive for lithium ion batteries according to the present invention is water-based by graft modification in an aqueous medium using polyvinyl alcohol or an acetal derivative thereof as a base polymer and two or more different polar monomers as graft copolymerization monomers. A polymer latex is formed, ie the aqueous polymer latex can be used as an adhesive for the electrode material.

本発明に係るリチウムイオン電池電極用水性接着剤の製造方法は以下の通りである。即ち、まず、ポリビニルアルコールおよびそのアセタール誘導体と、分散媒質としての蒸留水とを反応容器に入れ、完全に溶解するまで加熱しながら攪拌して混合させる。攪拌の速度は20〜700rpmであり、温度は60〜90℃である。更にグラフト共重合モノマーの一部分または全部を反応器の溶液中に加え、高純度の窒素ガスを通して酸素を0.5〜2時間排除させる。30〜90℃まで調節して一定に保ち、好ましくは40〜60℃である。開始剤を加え、グラフト共重合を開始させ、反応過程ではグラフト共重合モノマーの残余部分および追加する開始剤を連続滴下または数回に分けて加え、重合反応時間は5〜30時間であり、好ましくは15〜20時間である。反応を終了した後、真空により残余のモノマーを取り除くことで、リチウムイオン電池用電極材料の水性接着剤が得られた。その際、ベースポリマーとグラフト共重合モノマーとの重量比は30〜95：5〜70であり、好ましくは50〜70：50〜30である。   The method for producing the aqueous adhesive for lithium ion battery electrodes according to the present invention is as follows. That is, first, polyvinyl alcohol and its acetal derivative and distilled water as a dispersion medium are placed in a reaction vessel and mixed while stirring while heating until completely dissolved. The stirring speed is 20 to 700 rpm, and the temperature is 60 to 90 ° C. Further, some or all of the graft copolymerization monomer is added to the reactor solution and oxygen is purged through high purity nitrogen gas for 0.5-2 hours. The temperature is adjusted to 30 to 90 ° C and kept constant, preferably 40 to 60 ° C. An initiator is added to initiate graft copolymerization, and in the reaction process, the remainder of the graft copolymerization monomer and the initiator to be added are continuously added dropwise or divided into several times, and the polymerization reaction time is 5 to 30 hours, preferably Is 15-20 hours. After the reaction was completed, the remaining monomer was removed by vacuum to obtain an aqueous adhesive for a lithium ion battery electrode material. In that case, the weight ratio of the base polymer and the graft copolymerization monomer is 30 to 95: 5 to 70, preferably 50 to 70:50 to 30.

前記ベースポリマーは水溶性ポリビニルアルコールまたはそのアセタール誘導体であり、ポリビニルアルコール（またはそのアセタール誘導体）の重合度は1700〜2400の間、加水分解度は50〜99の間である。   The base polymer is water-soluble polyvinyl alcohol or its acetal derivative, and the degree of polymerization of polyvinyl alcohol (or its acetal derivative) is between 1700 and 2400, and the degree of hydrolysis is between 50 and 99.

前記グラフト共重合モノマーは、構造式がCHR1=CR2R3である二種以上の異なる極性のアルケンであり、その中、
R１=-Hまたは-CH３である。
R2=-H、-CH3または-COOLiである。
R3=-COOLi、-CONH2、-CONHCH3、-C6H5、-OCOCH3、-COOCH２CH２CH２CH3、-COOCH2CH(CH2CH3)CH２CH2CH2CH3または-CNである。 The graft copolymerization monomer is two or more different polar alkenes having the structural formula CHR 1 = CR 2 R 3 ,
R 1 = —H or —CH 3 .
R 2 = -H, -CH 3 or -COOLi.
R 3 = -COOLi, -CONH 2 , -CONHCH 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.

前記グラフト共重合モノマーは上記アルケン中の少なくとも一種とエポキシアルカンとの組み合わせでもよい。   The graft copolymerization monomer may be a combination of at least one of the above alkenes and an epoxy alkane.

前記反応で用いられた開始系は、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、アゾビスイソブチロニトリルなどの水溶性開始剤であり、または前記開始剤とNaHSO3、FeSO4などとから構成した酸化還元開始系である。開始剤の用量はモノマーの総重量の0.5〜1.5重量％である。 The initiator system used in the reaction is a water-soluble initiator such as ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, or composed of the initiator and NaHSO 3 , FeSO 4, etc. Redox initiation system. The initiator dose is 0.5-1.5% by weight of the total weight of monomers.

上記製造方法で得られたリチウムイオン電池用正極材料の水性接着剤の固形物の含有量の範囲は5〜40％（重量％であり、以下同様）であり、好ましくは10〜20％である。粘度は200〜20000センチポアズ（cP）（40℃）である。   The content range of the solid content of the aqueous adhesive of the positive electrode material for a lithium ion battery obtained by the above production method is 5 to 40% (% by weight, the same applies hereinafter), preferably 10 to 20%. . The viscosity is 200-20000 centipoise (cP) (40 ° C).

本発明では、リチウムイオン電池用水性接着剤に適用する正極材料は、LiFePO4、LiCoO2、LiNiO2、LiMn2O4およびその複数混合物などである。作られた電極シートでは、水性接着剤の含有量は2〜8重量％であり、好ましくは4〜6重量％である。 In the present invention, the positive electrode material applied to the aqueous adhesive for a lithium ion battery includes LiFePO 4 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4, and a mixture thereof. In the produced electrode sheet, the content of the aqueous adhesive is 2 to 8% by weight, preferably 4 to 6% by weight.

本発明で採用されたリチウムイオン電池用水性接着剤は、本分野の技術者が熟知するリチウムイオン電池製造プロセスに基づきリチウムイオン電池正極シートを製造し、且つアルミニウムプラスチック複合フィルムのフレキシブルパッケージの電池を組み立て、充放電を行い、測定結果を考察した。なお、その製造過程は以下の通りである。   The water-based adhesive for lithium ion batteries employed in the present invention produces a lithium ion battery positive electrode sheet based on a lithium ion battery production process familiar to those skilled in the art, and a flexible package battery of an aluminum plastic composite film. Assembly, charge and discharge were performed, and the measurement results were considered. The manufacturing process is as follows.

１．本発明のリチウムイオン電池正極用接着剤を濃度5重量％まで希釈し、希釈した当該接着剤60重量部を計量し、LiCoO2またはLiMn2O4正極粉末材料90重量部を加え、導電添加剤7重量部を混合させ、研磨してスラリーが得られ、清潔のアルミニウム箔上に均一に塗布し、乾燥して圧密することで、LiCoO2またはLiMn2O4正極電極シートが得られた。 1. The lithium ion battery positive electrode adhesive of the present invention is diluted to a concentration of 5% by weight, 60 parts by weight of the diluted adhesive is weighed, 90 parts by weight of LiCoO 2 or LiMn 2 O 4 positive electrode powder material is added, and a conductive additive 7 parts by weight was mixed and polished to obtain a slurry, which was uniformly coated on a clean aluminum foil, dried and consolidated, thereby obtaining a LiCoO 2 or LiMn 2 O 4 positive electrode sheet.

２．商品LA132水性接着剤を濃度5重量％まで希釈し、当該接着剤100重量部を計量し、炭素負極材料95重量部を加え、混合して、十分に研磨してスラリーが得られ、清潔の銅箔上に均一に塗布し、乾燥して圧密することで、負極電極シートが得られた。   2. The product LA132 water-based adhesive is diluted to a concentration of 5% by weight, 100 parts by weight of the adhesive is weighed, and 95 parts by weight of the carbon negative electrode material is added, mixed, and sufficiently polished to obtain a slurry. A negative electrode sheet was obtained by uniformly coating on the foil, drying and compacting.

３．作られたリチウムイオン電池正負極シートを電池容量の規格寸法に基づき所定の面積の電極シートを切断し、Cellgard-2400を電池の隔膜として、LiMn2O4／黒鉛またはLiCoO2／黒鉛の渦巻型リチウムイオン電池を製造し、アルミニウムプラスチック複合フィルムで封口し、温度80±10℃（８０℃プラスマイナス１０℃）で10〜48時間真空乾燥した後、乾燥したアルゴン雰囲気のグローブボックスに移動し、電解液を注入し、電解液はLiPF6／炭酸エチレン（EC）+炭酸ジエチル（DEC）+炭酸メチルエチル（EMC）であり、EC：DEC：EMC=1：1：1（重量比）である。電池測定は本分野の技術者が皆熟知するリチウムイオン電池の充放電の条件に基づき行う。 3. Lithium ion battery positive and negative electrode sheets are cut according to the standard dimensions of the battery capacity, the electrode sheet of the specified area is cut, and Cellgard-2400 is used as the battery diaphragm, and LiMn 2 O 4 / graphite or LiCoO 2 / graphite spiral type Lithium ion battery is manufactured, sealed with aluminum plastic composite film, vacuum dried at 80 ± 10 ° C (80 ° C plus or minus 10 ° C) for 10 to 48 hours, then moved to a dry argon atmosphere glove box for electrolysis The electrolyte is LiPF6 / ethylene carbonate (EC) + diethyl carbonate (DEC) + methyl ethyl carbonate (EMC), EC: DEC: EMC = 1: 1: 1 (weight ratio). The battery measurement is performed based on the charge / discharge conditions of the lithium ion battery, which are well known by engineers in this field.

以下、非限定性の実施例についてより詳細に説明し、本発明の理解に役立せる。本発明の保護範囲はこれらの実施例に限定されるものではない。本発明の保護範囲は請求項により決定するものである。   In the following, non-limiting examples will be described in more detail to aid in understanding the present invention. The protection scope of the present invention is not limited to these examples. The protection scope of the present invention is determined by the claims.

（実施例１）
リチウムイオン電池正極用水性接着剤の製造
本実施例では、水相でエポキシプロパン（POX）、アクリルアミド（AM）および酢酸ビニル（VAc）をポリビニルアルコール（PVA）とグラフト共重合させ、リチウムイオン電池正極シート用水性接着剤が作られた。その組成はPOX：AM：VAc：PVA=10：10：20：60（重量比であり、以下同様）であり、ラテックスの固形物の含有量は20重量％であり、生成物は薄白色のラテックスである。 Example 1
Production of Aqueous Adhesive for Lithium Ion Battery Positive Electrode In this example, lithium ion battery positive electrode was prepared by graft copolymerization of epoxypropane (POX), acrylamide (AM) and vinyl acetate (VAc) with polyvinyl alcohol (PVA) in the aqueous phase. A water based adhesive for the sheet was made. Its composition is POX: AM: VAc: PVA = 10: 10: 20: 60 (weight ratio, the same applies hereinafter), the latex solid content is 20% by weight, and the product is light white Latex.

上記リチウムイオン2次電池用水性接着剤の製造方法は以下の通りである。反応容器にポリビニルアルコール（重合度は1700、加水分解度99％である）60重量部と蒸留水400重量部を加え、95℃まで加熱し、攪拌して溶解させ、回転数は300rpmである。完全に溶解した後冷却し、且つ常に50℃に保つ。窒素ガスを通して酸素除去を2時間行い、エポキシプロパン10重量部、アクリルアミド10重量部および酢酸ビニル20重量部を加え、そして、過硫酸アンモニウム0.7重量部および亜硫酸ナトリウム0.4重量部を加え、12時間反応させて完了する。上記成分のリチウムイオン電池正極用水性接着剤が得られた。   The method for producing the water-based adhesive for lithium ion secondary batteries is as follows. In a reaction vessel, 60 parts by weight of polyvinyl alcohol (polymerization degree 1700, hydrolysis degree 99%) and 400 parts by weight of distilled water are added, heated to 95 ° C., dissolved by stirring, and the rotational speed is 300 rpm. Cool completely after dissolution and always keep at 50 ° C. Remove oxygen through nitrogen gas for 2 hours, add 10 parts by weight of epoxypropane, 10 parts by weight of acrylamide and 20 parts by weight of vinyl acetate, and then add 0.7 parts by weight of ammonium persulfate and 0.4 parts by weight of sodium sulfite and react for 12 hours. Complete. An aqueous adhesive for a lithium ion battery positive electrode having the above components was obtained.

（実施例２）
リチウムイオン電池正極用水性接着剤の製造
本実施例の接着剤の製造方法と操作条件は実施例１とほぼ同様であり、唯一異なるのは、エポキシプロパン（POX）をアクリロニトリル（AN）に代替する点である。反応容器にポリビニルアルコール60重量部と蒸留水400重量部を加え、完全に溶解した後、常に50℃に保つ。アクリルアミド15重量部、アクリロニトリル10重量部および酢酸ビニル15重量部を加え、20時間反応させて完了する。接着剤の組成はAM：AN：VAc：PVA=15：10：15：60（重量比）であり、ラテックスの固形物の含有量は20重量％であり、生成物は薄い黄白色のラテックスである。 (Example 2)
Manufacture of aqueous adhesive for lithium ion battery positive electrode The manufacturing method and operating conditions of the adhesive of this example are almost the same as those of Example 1. The only difference is that epoxipropane (POX) is replaced by acrylonitrile (AN). Is a point. After adding 60 parts by weight of polyvinyl alcohol and 400 parts by weight of distilled water to the reaction vessel and completely dissolving, keep the temperature at 50 ° C. 15 parts by weight of acrylamide, 10 parts by weight of acrylonitrile and 15 parts by weight of vinyl acetate are added and the reaction is completed for 20 hours. The composition of the adhesive is AM: AN: VAc: PVA = 15: 10: 15: 60 (weight ratio), the solid content of the latex is 20% by weight, and the product is a pale yellowish white latex is there.

（実施例３）
リチウムイオン電池正極用水性接着剤の製造
本実施例の接着剤の製造方法は実施例２とほぼ同様であり、唯一異なるのは、アクリル酸ブチル（BA）でアクリロニトリル（AN）を代替する点である。50℃で20時間反応させる。接着剤の組成はAM：BA：VAc：PVA=15：10：15：60（重量比）であり、ラテックスの固形物の含有量は20重量％であり、生成物は薄い黄白色のラテックスである。 (Example 3)
Production of aqueous adhesive for lithium ion battery positive electrode The production method of the adhesive of this example is almost the same as that of Example 2. The only difference is that butyl acrylate (BA) is substituted for acrylonitrile (AN). is there. The reaction is carried out at 50 ° C. for 20 hours. The composition of the adhesive is AM: BA: VAc: PVA = 15: 10: 15: 60 (weight ratio), the latex solid content is 20% by weight, and the product is a pale yellowish white latex is there.

（参考事例４）
リチウムイオン電池正極用水性接着剤の製造
本実施例の接着剤の製造方法は実施例２とほぼ同様であり、唯一異なるのは、アクリル酸エチルヘキシル（EHA）でアクリロニトリル（AN）を代替する点である。50℃で30時間反応させる。接着剤の組成はAM：EHA：VAc：PVA=15：10：15：60（重量比）であり、ラテックスの固形物の含有量は10重量％であり、生成物は白色のラテックスである。 ( Reference example 4)
Production method of the adhesive preparation embodiment of the lithium-ion battery cathode aqueous adhesive is substantially the same as in Example 2, the only difference is in that alternative acrylonitrile (AN) in ethyl hexyl acrylate (EHA) is there. The reaction is carried out at 50 ° C. for 30 hours. The composition of the adhesive is AM: EHA: VAc: PVA = 15: 10: 15: 60 (weight ratio), the latex solid content is 10% by weight, and the product is a white latex.

（参考事例５）
リチウムイオン電池正極用水性接着剤の製造
本実施例の接着剤の製造方法は実施例２とほぼ同様であり、唯一異なるのは、ベースポリマーはポリビニルブチラール（PVB）である。50℃で30時間反応させる。接着剤の組成はAM：AN：VAc：PVB=15：10：15：60（重量比）であり、ラテックスの固形物の含有量は10重量％であり、生成物は白色のラテックスである。 ( Reference Case 5)
Production of Aqueous Adhesive for Lithium Ion Battery Positive Electrode The production method of the adhesive of this example is almost the same as that of Example 2, and the only difference is that the base polymer is polyvinyl butyral (PVB). The reaction is carried out at 50 ° C. for 30 hours. The composition of the adhesive is AM: AN: VAc: PVB = 15: 10: 15: 60 (weight ratio), the content of latex solids is 10% by weight, and the product is white latex.

以下、本発明に係る水性接着剤はリチウムイオン電池に実際に応用するものである。   Hereinafter, the aqueous adhesive according to the present invention is actually applied to a lithium ion battery.

（実施例６）
本発明に係る水性接着剤を用いて製造される正極シートの性能パラメーター
LiCoO2とLiMn2O4とを正極材料として、実施例１〜３から得られたラテックスを接着剤として、導電剤を配合して、組成が正極材料90重量％、導電剤7重量％、接着剤3重量％である正極シートが作られた。正負極シートを整合し、リチウムイオン電池を組立てて、定電流充放電試験を行う。電池隔膜はCellgard-2400であり、電解液は1.0Mであり、LiPF6/EC+DEC+EMC（1：1：1）であり、実施例１〜３のラテックスを接着剤としての極シートパラメーターは表1に示す。その電池サイクル性を表2に示す。 (Example 6)
Performance parameters of the positive electrode sheet produced using the aqueous adhesive according to the present invention
LiCoO 2 and LiMn 2 O 4 were used as positive electrode materials, latex obtained from Examples 1 to 3 was used as an adhesive, and a conductive agent was blended. The composition was 90% by weight of the positive electrode material, 7% by weight of the conductive agent, and adhesion. A positive electrode sheet with 3% by weight of the agent was produced. The positive and negative electrode sheets are aligned, a lithium ion battery is assembled, and a constant current charge / discharge test is performed. The battery membrane is Cellgard-2400, the electrolyte is 1.0M, LiPF 6 / EC + DEC + EMC (1: 1: 1), and the polar sheet parameters using the latex of Examples 1 to 3 as an adhesive Is shown in Table 1. The battery cycle characteristics are shown in Table 2.

Figure 0005002052
Figure 0005002052

Figure 0005002052
Figure 0005002052

表１と表２の結果により、本発明に係るリチウムイオン電池正極用水性接着剤を用いて作られた正極は、LA132を用いた接着剤としての正極シートと比較して、圧密度が高く、リチウムイオン電池の体積エネルギー密度を著しく向上することができる。また、極シートの柔軟性は良好であり、電池製造の過程にとても有利であり、電池の歩留まりを大幅に向上することができる。且つ電池の充放電サイクル容量性は優れている。本発明はポリマーの改質方法を用いて、リチウムイオン電池に理想的な水性接着剤を提供する。   According to the results of Tables 1 and 2, the positive electrode made using the aqueous adhesive for a lithium ion battery positive electrode according to the present invention has a higher pressure density than the positive electrode sheet as an adhesive using LA132, The volume energy density of the lithium ion battery can be significantly improved. Further, the flexibility of the electrode sheet is good, which is very advantageous in the battery manufacturing process, and the yield of the battery can be greatly improved. Moreover, the charge / discharge cycle capacity of the battery is excellent. The present invention uses a polymer modification method to provide an aqueous adhesive ideal for lithium ion batteries.

Claims (9)

リチウムイオン電池用水性接着剤であって、
ポリビニルアルコールまたはそのアセタール誘導体をベースポリマーとし、二種以上の異なる極性のモノマーをグラフト共重合モノマーとして、水媒質中でグラフト改質することにより水性ポリマーラテックスを形成し、ラテックス中の固形物の含有量は5〜40重量％であり、その粘度は200〜20000センチポアズ（cP）（40℃で測定時）であり、
前記グラフト改質された水性ポリマーラテックスは、
ベースポリマーとしてのポリビニルアルコール（PVA）と、
第１のグラフト共重合モノマーとしてのエポキシプロパン（POX）、アクリロニトリル（AN）、又は、アクリル酸ブチル（BA）のいずれかと、
第２のグラフト共重合モノマーとしてのアクリルアミド（AM）と、
第３のグラフト共重合モノマーとしての酢酸ビニル（VAc）と、
をグラフト共重合させて得たものである、ことを特徴とするリチウムイオン電池正極用水性接着剤。A water-based adhesive for lithium ion batteries,
Aqueous polymer latex is formed by graft modification in an aqueous medium using polyvinyl alcohol or its acetal derivative as a base polymer, and two or more different polar monomers as graft copolymerization monomers, and solids are contained in the latex. The amount is 5-40% by weight, its viscosity is 200-20000 centipoise (cP) (when measured at 40 ° C) ,
The graft-modified aqueous polymer latex is
Polyvinyl alcohol (PVA) as a base polymer;
Either epoxy propane (POX), acrylonitrile (AN), or butyl acrylate (BA) as the first graft copolymerization monomer;
Acrylamide (AM) as the second graft copolymerization monomer,
Vinyl acetate (VAc) as a third graft copolymerization monomer;
A water-based adhesive for a lithium ion battery positive electrode , characterized by being obtained by graft copolymerization . 前記ベースポリマーのポリビニルアルコールまたはそのアセタール誘導体の重合度は1700〜2400の間、加水分解度は50〜99の間であることを特徴とする請求項１記載のリチウムイオン電池正極用水性接着剤。The aqueous adhesive for a lithium ion battery positive electrode according to claim 1, wherein the polyvinyl alcohol or acetal derivative thereof as the base polymer has a polymerization degree of 1700-2400 and a hydrolysis degree of 50-99. 請求項１または２に記載のリチウムイオン電池正極用水性接着剤の製造方法であって、以下の（１）、（２）、（３）、（４）のステップが含まれること、即ち、
（１）ベースポリマーとグラフト共重合モノマーとの重量比（ベースポリマー／グラフト共重合モノマー）が、３０／７０〜９５／５であることに基づいて原料を計量し、
（２）ベースポリマーと蒸留水とを反応容器に入れ、完全に溶解するまで加熱しながら攪拌し、温度は60〜90℃であり、
（３）すべてのグラフト共重合モノマーを反応器の溶液中に加え、高純度の窒素ガスを通して酸素を0.5〜2時間排除させ、30〜90℃まで調節して一定に保ち、
（４）開始剤を加え、グラフト共重合を開始させ、重合反応時間は5〜30時間であり、反応を終了した後、真空により残余のモノマーを取り除くことで、リチウムイオン電池正極用水性接着剤を得る、
ことを特徴とするリチウムイオン電池正極用水性接着剤の製造方法。 It is a manufacturing method of the water-based adhesive for lithium ion battery positive electrodes of Claim 1 or 2, Comprising : The following (1), (2), (3), (4) steps are included, ie,
(1) The raw material is weighed based on the weight ratio of the base polymer to the graft copolymerization monomer (base polymer / graft copolymerization monomer) being 30/70 to 95/5 ,
(2) Put the base polymer and distilled water in a reaction vessel, stir while heating until completely dissolved, the temperature is 60-90 ° C,
(3) Add all the graft copolymerization monomers into the reactor solution, let oxygen escape for 0.5-2 hours through high purity nitrogen gas, adjust to 30-90 ° C and keep constant,
(4) An initiator is added to initiate graft copolymerization, and the polymerization reaction time is 5 to 30 hours. After the reaction is completed, the remaining monomer is removed by vacuum to obtain an aqueous adhesive for a lithium ion battery positive electrode. Get the
The manufacturing method of the water-based adhesive for lithium ion battery positive electrodes characterized by the above-mentioned. 重合反応を段階的に行うために、前記第三ステップでは一部分のグラフト共重合モノマーを加え、グラフト共重合モノマーの残余の部分を前記第四ステップの重合反応過程において滴下または数回に分けて加えると同時に、開始剤を追加で添加する、
ことを特徴とする請求項３に記載のリチウムイオン電池正極用水性接着剤の製造方法。In order to perform the polymerization reaction step by step, a part of the graft copolymerization monomer is added in the third step, and the remaining part of the graft copolymerization monomer is added dropwise or divided into several times in the polymerization reaction process of the fourth step. At the same time, additional initiator is added,
The manufacturing method of the water-based adhesive for lithium ion battery positive electrodes of Claim 3 characterized by the above-mentioned. 前記反応で用いられた開始系は、過硫酸アンモニウム、過硫酸カリウム、過酸化水素もしくはアゾビスイソブチロニトリルから選択される水溶性開始剤であり、または前記開始剤とNaHSO3もしくはFeSO4 とで構成された酸化還元開始系であり、開始剤の用量はモノマーの総重量の0.5〜1.5重量％である、ことを特徴とする請求項３または４に記載のリチウムイオン電池正極用水性接着剤の製造方法。Initiation system used in the reaction, ammonium persulfate, potassium persulfate, a water soluble initiator selected from hydrogen peroxide or azobisisobutyronitrile, or with the initiator and NaHSO 3 or FeSO 4 5. The water-based adhesive for a lithium ion battery positive electrode according to claim 3 , wherein the redox initiator system is configured, and the dose of the initiator is 0.5 to 1.5% by weight of the total weight of the monomers. Production method. 重合反応の温度は40〜60℃であり、重合反応の時間は15〜20時間であることを特徴とする請求項３または４に記載のリチウムイオン電池正極用水性接着剤の製造方法。5. The method for producing an aqueous adhesive for a lithium ion battery positive electrode according to claim 3 , wherein the temperature of the polymerization reaction is 40 to 60 ° C., and the time of the polymerization reaction is 15 to 20 hours. ラテックスの固形物の含有量は10〜20重量％であり、粘度は200〜20000センチポアズ（cP）（40℃）であることを特徴とする請求項３または４に記載のリチウムイオン電池正極用水性接着剤の製造方法。The content of solids of the latex is 10 to 20 wt%, a viscosity of 200 to 20,000 centipoise (cP) (40 ℃) lithium-ion battery cathode water of claim 3 or 4, characterized in that it is Manufacturing method of adhesive. リチウムイオン電池の正極用の極シートであって、請求項１または２に記載のリチウムイオン電池正極用水性接着剤と、リチウムイオン電池正極粉末材料と、導電剤から作られ、その中で、水性接着剤の含有量は2〜8重量％である、ことを特徴とするリチウムイオン電池の正極極シート。 An electrode sheet for a positive electrode of a lithium ion battery, which is made of the aqueous adhesive for a lithium ion battery positive electrode according to claim 1 or 2, a lithium ion battery positive electrode powder material, and a conductive agent , The positive electrode sheet of a lithium ion battery, wherein the content of the adhesive is 2 to 8% by weight. 水性接着剤の含有量は4〜6重量％であることを特徴とする請求項８に記載のリチウムイオン電池の正極極シート。The positive electrode sheet for a lithium ion battery according to claim 8, wherein the content of the aqueous adhesive is 4 to 6% by weight.
JP2010503344A 2008-03-18 2009-02-18 Aqueous adhesive for lithium ion battery, method for producing the same, and lithium ion battery positive electrode sheet Active JP5002052B2 (en)

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