JPH09306474A - Applying paste for electrode and nonaqueous secondary battery electrode - Google Patents

Applying paste for electrode and nonaqueous secondary battery electrode

Info

Publication number
JPH09306474A
JPH09306474A JP8157339A JP15733996A JPH09306474A JP H09306474 A JPH09306474 A JP H09306474A JP 8157339 A JP8157339 A JP 8157339A JP 15733996 A JP15733996 A JP 15733996A JP H09306474 A JPH09306474 A JP H09306474A
Authority
JP
Japan
Prior art keywords
weight
propylene
electrode
active material
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8157339A
Other languages
Japanese (ja)
Inventor
Kazuo Tagawa
和男 田川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP8157339A priority Critical patent/JPH09306474A/en
Publication of JPH09306474A publication Critical patent/JPH09306474A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide appropriate viscosity, and safely and easily manufacture electrodes by using an aqueous dispersing element composed of a battery active material and a specific organic compound and to provide a superior battery performance by reducing swelling property of the electrodes to electrolyte. SOLUTION: An aqueous dispersing element containing a battery active material 98.5-85wt.%, copolymer of propylene and tetrafluoroethylene 0.1-13wt.%, carboxymethyl cellulose group 0.2-2wt.%, and polyacrylic acid group 0-1wt.% is used for paste. As propylene-fluorocarbon copolymer copolymer of them and vinylidene fluoride is used as substitute for it or as mixture of them. This constitution can eliminate any necessity solvent and need only volatility of water in an industrial coating process. Metal oxide, metal sulfide, or lithium compound metal oxide, or the like is used for a positive electrode active material, carbonaceous material, etc., is used for a negative electrode active material, and their mean particle size is preferable to be 3-20μm.

Description

【発明の詳細な説明】Detailed Description of the Invention

［産業上の利用分野］本発明は、非水系二次電池の電極
に関する。[Field of Industrial Application] The present invention relates to an electrode of a non-aqueous secondary battery.

【０００３】［従来の技術及び問題点］近年、電子機器
の進展はめざましく、携帯用電子機器の小型化、軽量化
が急速に進行している。これらの電源となる電池にも小
型、軽量となる高エネルギー密度が要求されている。中
でも非水系二次電池として、リチウムあるいはリチウム
合金を負極に用い、電解液含浸固体電解質を用いた二次
電池、炭素質材料を負極に用いたリチウムイオン二次電
池が注目されている。かかる非水系二次電池は、電子機
器の比較的消費電流の大きい電源に使用されることが多
く、電極を薄膜化し、電極面積を大きくする必要があ
る。従来、電極の成形方法として、電池活物質粉末をテ
フロン粉末、ポリエチレン粉末等の粉末状バインダーと
共に混合し、圧縮成形することができるが、薄膜・大面
積の電極を調製することには困難を伴う。一方、ブタジ
エン系ゴム、ＥＰＤＭゴムは、有機溶剤溶液あるいは水
に乳化・分散したラテックスとして電池活物質粉末を加
えて分散した後、集電体である金属箔上に、塗布・乾燥
することにより電極を形成する方法も提案されている。
この方法によれば、薄膜・大面積の電極が容易に得られ
る利点がある。反面、絶縁性物質であるバインダーは、
金属箔との密着性を高めると、電極として電池の著しい
過電圧の上昇をまねき、実用上、必ずしも満足できるも
のではなかった。ポリフッ化ビニリデンがかかる問題点
を解決する方法として提案されているが、溶剤として、
Ｎ−メチルピロリドン，ジメチルアセトアミド，ヘキサ
メチルホスホアミド，ジメチルスルホキシド等の沸点が
高く、極性の強く、残存すると電池特性に悪影響を及ぼ
しやすく、中には毒性の強いものも含まれている。ま
た、フッ化ビニリデン，ヘキサフロロプロピレン，四フ
ッ化エチレンからなるフッ素系高分子共重合体は、通常
の塗工溶剤に容易に溶けて安定なバインダー溶液を与え
るとされている。しかるに、プロピレンカーボネート，
２−メチルテトラヒドロフラン，γ−ブチロラクトン等
の通常用いられる電解液中で６０℃以上において、放置
時に、電池容量低下を招くことがある。[Prior Art and Problems] In recent years, electronic devices have made remarkable progress, and portable electronic devices have been rapidly reduced in size and weight. Batteries used as these power sources are also required to have high energy density which is small and lightweight. Among them, as non-aqueous secondary batteries, attention has been paid to secondary batteries using lithium or a lithium alloy for a negative electrode and an electrolyte impregnated solid electrolyte, and lithium ion secondary batteries using a carbonaceous material for the negative electrode. Such a non-aqueous secondary battery is often used as a power source for electronic devices that consumes a relatively large amount of current, and it is necessary to thin the electrodes and increase the electrode area. Conventionally, as a method for forming an electrode, a battery active material powder can be mixed with a powdery binder such as Teflon powder or polyethylene powder and compression-molded, but it is difficult to prepare a thin film / large-area electrode. . On the other hand, butadiene-based rubber and EPDM rubber are dispersed by adding a battery active material powder as a latex emulsified and dispersed in an organic solvent solution or water, and then coating and drying it on a metal foil as a current collector to form an electrode. A method of forming the is also proposed.
According to this method, there is an advantage that a thin film and a large area electrode can be easily obtained. On the other hand, the binder, which is an insulating material,
Increasing the adhesion to the metal foil leads to a marked increase in overvoltage of the battery as an electrode, which is not always satisfactory in practical use. Polyvinylidene fluoride has been proposed as a method for solving such problems, but as a solvent,
N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoamide, dimethylsulfoxide, and the like have high boiling points and strong polarities, and if they remain, they tend to adversely affect the battery characteristics, and some of them are highly toxic. A fluoropolymer copolymer composed of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene is said to be easily dissolved in an ordinary coating solvent to give a stable binder solution. However, propylene carbonate,
At 60 ° C. or higher in a commonly used electrolytic solution such as 2-methyltetrahydrofuran or γ-butyrolactone, the capacity of the battery may decrease when left standing.

【０００４】［発明が解決しようとする問題点］前述の
如く、電極の調製の方法として、実用上 １）溶剤の沸点が比較的低く、乾燥が容易であること。
２）毒性が小さいこと。３）溶剤コストが低いこと。
４）バインダーは、溶剤には、溶解し、乾燥後は、電解
液には、不溶ないし低い膨潤性を示すものが望ましく、
電極として電池活物質の実用性能が発揮されること。
５）金属箔へ一度に塗布し乾燥するにあたり５０〜２０
０μｍの薄膜を得るために十分な粘稠性を有すること等
すべてを満足するものがないのが現状である。[Problems to be Solved by the Invention] As described above, as a method for preparing an electrode, in practice, 1) the boiling point of the solvent is relatively low and the drying is easy.
2) Low toxicity. 3) Low solvent cost.
4) It is desirable that the binder be soluble in a solvent and insoluble or have a low swelling property in an electrolytic solution after drying.
The practical performance of the battery active material should be demonstrated as an electrode.
5) 50 to 20 for coating and drying metal foil at once
At present, there is no one that satisfies all requirements such as having sufficient viscosity to obtain a thin film of 0 μm.

【０００５】［発明が解決しようとする課題］本発明
は、かかる問題点を解決し、工業的塗工プロセスにおい
て容易に電極が製造できる電極用塗布液と優れた電池性
能を有する非水二次電池電極の提供を目的とする。[Problems to be Solved by the Invention] The present invention solves the above problems, and a non-aqueous secondary liquid having excellent battery performance and an electrode coating liquid for easily manufacturing electrodes in an industrial coating process. The purpose is to provide a battery electrode.

【０００６】［問題点を解決するための手段］本発明
は、電池活物質を９８．５重量％〜８５重量％とプロピ
レンと四フッ化エチレンとの共重合体、及び又はプロピ
レンと四フッ化エチレンとフッ化ビニリデンとの共重合
体のプロピレン−フッソ系共重合体類を０．１重量％〜
１３重量％とカルボキシメチルセルロース類０．２重量
％〜２重量％とポリアクリル酸類０重量％〜１．０重量
％を含んでなる水性分散体である電極用塗布ペーストと
電池活物質を９８．５重量％〜８５重量％とプロピレン
と四フッ化エチレンとの共重合体、及び又はプロピレン
と四フッ化エチレンとフッ化ビニリデンとの共重合体の
プロピレン−フッソ系共重合体類を０．１重量％〜１３
重量％とカルボキシメチルセルロース類０．２重量％〜
２重量％とポリアクリル酸類０重量％〜１．０重量％を
含んでなる非水系二次電池電極とすることにある。該プ
ロピレン−フッソ系共重合体類を、水に乳化ないし分散
して、水性分散液を用いることにより溶剤を不用とす
る。カルボキシメチルセルロース類とポリアクリル酸類
の水溶液と共に電池活物質粉末と混合し、塗工に十分な
適度な粘稠なペーストをつくることができ、工業的塗工
プロセスにおいて水を揮散させるのみで作業安全性も高
く容易に電極が、製造できる。またかかる電極は、電解
液に極めて低い膨潤性を示し、優れた電池性能を有す
る。[Means for Solving the Problems] In the present invention, a battery active material of 98.5 wt% to 85 wt% and a copolymer of propylene and tetrafluoroethylene, and / or propylene and tetrafluoride are used. 0.1% by weight of propylene-fluorine-based copolymers of ethylene and vinylidene fluoride
98.5% of the electrode coating paste and the battery active material, which are aqueous dispersions containing 13% by weight, 0.2% by weight to 2% by weight of carboxymethylcellulose and 0% to 1.0% by weight of polyacrylic acid. 0.1% by weight of propylene-fluorine-based copolymers of propylene-tetrafluoroethylene copolymer and / or propylene-tetrafluoroethylene-vinylidene fluoride copolymer. % ~ 13
Wt% and carboxymethylcelluloses 0.2 wt% ~
The non-aqueous secondary battery electrode contains 2% by weight and 0% to 1.0% by weight of polyacrylic acid. The propylene-fluorine-based copolymers are emulsified or dispersed in water and an aqueous dispersion is used to eliminate the need for a solvent. By mixing with an aqueous solution of carboxymethyl cellulose and polyacrylic acid together with the battery active material powder, a viscous paste that is suitable for coating can be prepared, and work safety is achieved by simply evaporating water in an industrial coating process. Electrodes can be manufactured with high cost. Further, such an electrode shows extremely low swelling property in an electrolytic solution and has excellent battery performance.

【０００７】本発明で用いられる電池活物質は、特に限
定されるものではないが、一例を示せば、ＭｎＯ２、Ｖ
２Ｏ５、Ｖ６Ｏ１３等の金属酸化物、ＴｉＳ２、ＭｏＳ
２、ＦｅＳ等の金属硫化物、ＬｉＣｏＯ２、ＬｉＮｉＯ
２、ＬｉＭｎ２Ｏ４等のＣｏ，Ｎｉ，Ｍｎ，Ｆｅ，Ｔｉ
等の遷移金属を主成分とするリチウム複合金属酸化物等
の正極活物質、コークス、グラファイト、メソフェーズ
ピッチ小球体、フェノール樹脂、ポリパラフェニレン等
の高分子の炭化物、気相生成カーボンファイバー、炭素
繊維等の炭素質材料の負極活物質がある。本発明で用い
られる電池活物質の平均粒子系は、良好な電極性能を得
る上で、１〜５０μｍ、好ましくは、３〜２０μｍであ
る。本発明のプロピレン−フッソ系共重合体類とは、乳
化剤又は／及び分散剤を用いてプロピレンと四フッ化エ
チレン、プロピレンと四フッ化エチレンとフッ化ビニリ
デンを主成分としてラジカル重合して得られる。本発明
のカルボキシメチルセルロース類とは、カルボキシメチ
ルセルロース（Ｌｉ、Ｎａ、Ｋ、ＮＨ４塩）あるいはこ
れらのいずれかを主成分としメチルセルロース、エチル
セルロース、ヒドロキシメチルセルロース、ポリビニル
アルコール、酸化スターチ、燐酸化スターチ等の１種又
は２種以上との混合物である。本発明のポリアクリル酸
類とは、ポリアクリル酸、ポリアクリル酸の塩（Ｌｉ、
Ｎａ、Ｋ、ＮＨ４）、メタクリル酸、イタコン酸、マレ
イン酸等のポリマーあるいはこれらのいずれのポリマー
の前記塩、アクリル酸（塩）、メタクリル酸（塩）、イ
タコン酸（塩）、マレイン酸（塩）等を主成分とし、共
重合可能なモノマーとの水溶性ポリマーである。必要に
応じて、ピロ燐酸Ｎａ等の燐酸系分散剤、ノニルフェノ
ールのエチレンオキサイド付加物等のノニオン系界面活
性剤、ラウリル硫酸Ｎａ等のアニオン系界面活性剤を添
加しても良い。The battery active material used in the present invention is not particularly limited, but MnO 2 and V can be given as an example.
2 O 5 , V 6 O 13 and other metal oxides, TiS 2 , MoS
2 , metal sulfides such as FeS, LiCoO 2 , LiNiO
2 , Co, Ni, Mn, Fe, Ti such as LiMn 2 O 4
Positive electrode active materials such as lithium composite metal oxides containing transition metals as main components, coke, graphite, mesophase pitch spherules, phenolic resins, polymer carbides such as polyparaphenylene, vapor-grown carbon fibers, carbon fibers There is a negative electrode active material such as a carbonaceous material. The average particle size of the battery active material used in the present invention is from 1 to 50 μm, preferably from 3 to 20 μm in order to obtain good electrode performance. The propylene-fluorine-based copolymers of the present invention are obtained by radical polymerization using propylene and tetrafluoroethylene, propylene, tetrafluoroethylene and vinylidene fluoride as main components using an emulsifier and / or a dispersant. . The carboxymethyl celluloses of the present invention include carboxymethyl cellulose (Li, Na, K, NH 4 salt) or any one of them as a main component, such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohol, oxidized starch and phosphorylated starch. It is a mixture of two or more species. The polyacrylic acids of the present invention include polyacrylic acid and salts of polyacrylic acid (Li,
Na, K, NH 4 ), polymers such as methacrylic acid, itaconic acid, maleic acid and the like, or salts of any of these polymers, acrylic acid (salt), methacrylic acid (salt), itaconic acid (salt), maleic acid ( It is a water-soluble polymer having a salt as a main component and a copolymerizable monomer. If necessary, a phosphoric acid dispersant such as Na pyrophosphate, a nonionic surfactant such as an ethylene oxide adduct of nonylphenol, and an anionic surfactant such as Na lauryl sulfate may be added.

【０００８】本発明の塗布ペーストは、前記プロピレン
−フッソ系共重合体類の水性分散液と前記カルボキシメ
チルセルロース類の水溶液と前記ポリアクリル酸類の水
溶液とを所定の比率範囲で混合される。混合には、特に
限定されるものではなく、通常の撹拌機が、使用でき
る。電池活物質を９８．５重量％〜８５重量％とプロピ
レンと四フッ化エチレンとの共重合体、及び又はプロピ
レンと四フッ化エチレンとフッ化ビニリデンとの共重合
体のプロピレン−フッソ系共重合体類を０．１重量％〜
１３重量％とカルボキシメチルセルロース類０．２重量
％〜２重量％とポリアクリル酸類０重量％〜１．０重量
％を含んでなる水性分散体である。本発明の集電体の金
属箔としては、アルミニウム、ニッケル、ステンレスス
チール、銅の金属箔、金属網状物、金属多孔体等の１μ
ｍ〜１００μｍの厚みのものが用いられる。本発明の非
水系二次電池電極は、前記塗布ペーストを、前記金属箔
に、ドクターブレード法、各種コーター法、グラビヤ法
等の任意の方法で塗布し、絶乾し、電極を得る。必要な
らば、更にプレスしてもよい。本発明の塗布ペースト及
び非水系二次電池電極は、電池活物質を９８．５重量％
〜８５重量％とプロピレンと四フッ化エチレンとの共重
合体、及び又はプロピレンと四フッ化エチレンとフッ化
ビニリデンとの共重合体のプロピレン−フッソ系共重合
体類を０．１重量％〜１３重量％とカルボキシメチルセ
ルロース類０．２重量％〜２重量％とポリアクリル酸類
０重量％〜１．０重量％を含んでなる非水系二次電池電
極とすることにある。電池活物質が、９８．５重量％を
越えると集電体への接着が、悪くなり充放電サイクル寿
命に劣る。また８５重量％未満では、電池として、体積
当たりの容量の観点で劣り好ましくない。In the coating paste of the present invention, an aqueous dispersion of the propylene-fluorine-based copolymers, an aqueous solution of the carboxymethyl celluloses and an aqueous solution of the polyacrylic acids are mixed in a predetermined ratio range. The mixing is not particularly limited, and a general stirrer can be used. Propylene-fluoride copolymer copolymer of 98.5 wt% to 85 wt% of a battery active material, a copolymer of propylene and tetrafluoroethylene, and / or a copolymer of propylene, tetrafluoroethylene and vinylidene fluoride. 0.1% by weight of coalesce
It is an aqueous dispersion containing 13% by weight, 0.2% by weight to 2% by weight of carboxymethyl cellulose and 0% to 1.0% by weight of polyacrylic acid. As the metal foil of the current collector of the present invention, 1 μm of aluminum, nickel, stainless steel, copper metal foil, metal mesh, metal porous body, etc.
Those having a thickness of m to 100 μm are used. In the non-aqueous secondary battery electrode of the present invention, the coating paste is applied to the metal foil by an arbitrary method such as a doctor blade method, various coater methods or a gravure method, and dried to obtain an electrode. Further pressing may be performed if necessary. The coating paste and the non-aqueous secondary battery electrode of the present invention contain 98.5% by weight of the battery active material.
~ 85 wt% propylene-tetrafluoroethylene copolymer and / or propylene-tetrafluoroethylene vinylidene fluoride copolymer propylene-fluorine copolymer 0.1 wt% ~ A non-aqueous secondary battery electrode comprising 13% by weight, 0.2% by weight to 2% by weight of carboxymethylcellulose and 0% to 1.0% by weight of polyacrylic acid. If the amount of the battery active material exceeds 98.5% by weight, the adhesion to the current collector will be poor and the charge / discharge cycle life will be poor. If it is less than 85% by weight, the battery is inferior in terms of capacity per volume, which is not preferable.

【０００９】本発明の電極に使用する電解液は、非プロ
トン性有機溶媒、例えばプロピレンカーボネート、エチ
レンカーボネート、ジメチルカーボネート、エチルメチ
ルカーボネート、ジエチルカーボネート、γ−ブチロラ
クトン、ジエトキシエタン等がある。電解塩としてはＬ
ｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＡｓＦ５、
ＣＦ３ＳＯ３Ｌｉ、（ＣＦ３ＳＯ２）２ＮＬｉ等のリチ
ウム塩からなる。本発明の電極は、円筒形、シート形、
角形等の任意の形状にして電池に用いられる。The electrolytic solution used for the electrode of the present invention includes an aprotic organic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, γ-butyrolactone and diethoxyethane. L as an electrolytic salt
iClO 4 , LiBF 4 , LiPF 6 , LiAsF 5 ,
It is composed of a lithium salt such as CF 3 SO 3 Li or (CF 3 SO 2 ) 2 NLi. The electrode of the present invention has a cylindrical shape, a sheet shape,
It is used for a battery by making it into an arbitrary shape such as a prism.

【００１０】［実施例］以下に本発明の実施例を説明す
る。但し、以下に示す実施例は、本発明の例示であって
本発明の電極は、これらに限定されるものではない。 ［実施例１］プロピレン，四フッ化エチレンとの共重合
体（モル比４５：５５）ラテックス（固形分３１．４重
量％）３．６重量部とカルボキシメチルセルロースＬｉ
の０．８９５重量％の水溶液９５．０重量部とポリアク
リル酸水溶液（固形分１０重量％）０．２２重量部とを
あらかじめ混合した液中に平均粒子径１０μｍのニード
ルコークス９８．０重量部を撹拌しながら加える。表面
を粗くした１２μｍの銅箔に膜厚９５μｍになるように
塗布する。１１０℃で絶乾する。これを１．５ｃｍ×
２．０ｃｍに切り出し、負極とする。 ［実施例２］プロピレン，四フッ化エチレン，フッ化ビ
ニリデン（モル比２５：４Ｐ：３５）との共重合体ラテ
ックス（固形分３２．３重量％）３．５重量部とカルボ
キシメチルセルロースＮａの０．９重量％の水溶液９
５．０重量部とポリアクリル酸水溶液（固形分１０重量
％）０．２２重量部とをあらかじめ混合した液中に平均
粒子径８μｍのＬｉＣｏＯ２９１．５重量部，アセチレ
ンブラック０．５重量部，黒鉛粉末６．０重量部とを予
備混合したものを混合撹拌する。これを、アセチレンブ
ラックとカルボキシ変性ゴムとからなるトルエン溶液に
よりプライマー処理された表面を有する１５μｍのアル
ミ箔に塗布する。１２０℃の乾燥機に入れて絶乾する。
膜厚は、１２５μｍとする。これを１．５ｃｍ×２．０
ｃｍに切り出し正極とする。 ［実施例３］プロピレン，四フッ化エチレンとの共重合
体（モル比４５：５５）ラテックス（固形分３１重量
％）３．６重量部とカルボキシメチルセルロースＮａの
０．９０重量％の水溶液９４．４重量部とポリアクリル
酸水溶液（固形分１０重量％）０．２２重量部とをあら
かじめ混合した液中に平均粒子径５μｍの人工グラファ
イト９８．０重量部を撹拌しながら加える。表面を粗く
した１２μｍの銅箔に膜厚９５μｍになるように塗布す
る。１１０℃で絶乾する。これを１．５ｃｍ×２．０ｃ
ｍに切り出し負極とする。 ［実施例４］プロピレン，四フッ化エチレン，フッ化ビ
ニリデン（モル比２５：４０：３５）との共重合体ラテ
ックス（固形分３２．３重量％）３．５重量部とカルボ
キシメチルセルロースＮａの０．９重量％の水溶液９
５．０重量部とポリアクリル酸水溶液（固形分１０重量
％）０．２２重量部とをあらかじめ混合した液中に平均
粒子径１５μｍのＬｉＭｎ２Ｏ４９１．５重量部，アセ
チレンブラック０．５重量部，黒鉛粉末６．０重量部と
を予備混合したものを混合撹拌する。これを、実施例２
と同一のアルミ箔に塗布する。１２０℃の乾燥機に入れ
て絶乾する。膜厚は、１１５μｍとなるようにする。こ
れを１．５ｃｍ×２．０ｃｍに切り出し正極とする。 ［比較例１］実施例１と同一のニードルコークス９６重
量部をポリフッ化ビニリデン４重量部をＮ−メチルピロ
リドン９６．０重量部に溶解した液と混合撹拌する。こ
れを表面を粗くした１２μｍの銅箔に塗布し、膜厚９０
μｍとする。１６０℃の乾燥機に入れて乾燥する。１．
５ｃｍ×２．０ｃｍに切り出し負極とする。 ［比較例２］実施例２と同一のＬｉＣｏＯ２，アセチレ
ンブラック，黒鉛微粉末の予備混合品９６重量部とポリ
フッ化ビニリデン４重量部をＮ−メチルピロリドン９
６．０重量部とを混合し撹拌するこれを１５μｍのアル
ミ箔にドクターブレートで塗布する。１６０℃の乾燥機
にいれて乾燥する。膜厚は１３０μｍであり、１．５ｃ
ｍ×２．０ｃｍに切り出し正極とする。 実施例１〜
４及び比較例１〜２ともいずれも対極は、リチウム金属
箔を銅ネットに押しつけたものを用いて、多孔質ポリエ
チレンセパレーター（２５μｍ）を介在し、電解液１Ｍ
ＬｉＰＦ６のエチルメチルカーボネート−エチレンカー
ボネート（体積比３：１）の電池として過電圧を測定す
る。初回の放電容量に対して充放電サイクル１０回目の
放電容量を容量保持率として求める。結果をまとめて表
１に示す。 [Embodiment] An embodiment of the present invention will be described below. However, the examples described below are examples of the present invention, and the electrodes of the present invention are not limited thereto. [Example 1] 3.6 parts by weight of a copolymer of propylene and tetrafluoroethylene (molar ratio 45:55) latex (solid content: 31.4% by weight) and carboxymethylcellulose Li
95.0 parts by weight of an aqueous solution of 0.895% by weight and 0.22 parts by weight of an aqueous solution of polyacrylic acid (solid content: 10% by weight) are mixed in advance in a solution of 98.0 parts by weight of needle coke having an average particle diameter of 10 μm. Is added with stirring. A copper foil having a roughened surface and a thickness of 12 μm is applied so as to have a film thickness of 95 μm. Dry at 110 ° C. 1.5 cm x this
Cut out to 2.0 cm and use as a negative electrode. [Example 2] 3.5 parts by weight of copolymer latex (solid content 32.3% by weight) with propylene, tetrafluoroethylene, vinylidene fluoride (molar ratio 25: 4P: 35) and 0 of carboxymethylcellulose Na. 9% by weight aqueous solution 9
91.5 parts by weight of LiCoO 2 having an average particle diameter of 8 μm and 0.5 part by weight of acetylene black in a liquid prepared by previously mixing 5.0 parts by weight and 0.22 part by weight of an aqueous solution of polyacrylic acid (solid content: 10% by weight). And 6.0 parts by weight of graphite powder are mixed in advance and mixed and stirred. This is applied to a 15 μm aluminum foil having a surface primed with a toluene solution consisting of acetylene black and a carboxy modified rubber. Put in a dryer at 120 ° C to dry completely.
The film thickness is 125 μm. 1.5 cm x 2.0
Cut out to cm and use as a positive electrode. [Example 3] 3.6 parts by weight of a copolymer (molar ratio 45:55) latex (solid content 31% by weight) of propylene and tetrafluoroethylene and 0.90% by weight aqueous solution of carboxymethylcellulose Na 94. 98.0 parts by weight of artificial graphite having an average particle diameter of 5 μm is added to a liquid in which 4 parts by weight and 0.22 part by weight of a polyacrylic acid aqueous solution (solid content 10% by weight) are mixed in advance. A copper foil having a roughened surface and a thickness of 12 μm is applied so as to have a film thickness of 95 μm. Dry at 110 ° C. 1.5 cm x 2.0 c
Cut out to m to make a negative electrode. Example 4 3.5 parts by weight of copolymer latex (solid content 32.3% by weight) with propylene, tetrafluoroethylene, vinylidene fluoride (molar ratio 25:40:35) and 0 of carboxymethylcellulose Na. 9% by weight aqueous solution 9
5.0 parts by weight and 0.22 parts by weight of a polyacrylic acid aqueous solution (solid content: 10% by weight) were mixed in advance in a solution, 91.5 parts by weight of LiMn 2 O 4 having an average particle diameter of 15 μm, and 0.5 parts of acetylene black. Preliminarily mixed parts by weight and 6.0 parts by weight of graphite powder are mixed and stirred. Example 2
Apply to the same aluminum foil as. Put in a dryer at 120 ° C to dry completely. The film thickness is set to 115 μm. This is cut out into 1.5 cm × 2.0 cm and used as a positive electrode. [Comparative Example 1] The same needle coke as in Example 1 (96 parts by weight) was mixed and stirred with a solution prepared by dissolving 4 parts by weight of polyvinylidene fluoride in 96.0 parts by weight of N-methylpyrrolidone. Apply this to a roughened 12 μm copper foil to give a film thickness of 90
μm. Put in a dryer at 160 ° C to dry. 1.
Cut out into 5 cm × 2.0 cm to make a negative electrode. [Comparative Example 2] The same LiCoO 2 , acetylene black, and 96 parts by weight of a fine graphite powder as in Example 2 and 4 parts by weight of polyvinylidene fluoride were added to N-methylpyrrolidone 9
6.0 parts by weight are mixed and stirred This is applied to a 15 μm aluminum foil with a doctor plate. Put in a dryer at 160 ° C to dry. The film thickness is 130 μm, 1.5c
Cut out into m × 2.0 cm to make a positive electrode. Example 1
4 and Comparative Examples 1 and 2, the counter electrode was prepared by pressing a lithium metal foil against a copper net, with a porous polyethylene separator (25 μm) interposed, and an electrolytic solution 1M.
The overvoltage is measured as a LiPF 6 ethylmethylcarbonate-ethylenecarbonate (volume ratio 3: 1) battery. The discharge capacity at the 10th charge / discharge cycle with respect to the initial discharge capacity is determined as the capacity retention rate. The results are summarized in Table 1.

【００１１】［発明の効果］表１の如く、本発明の塗布
液によりつくられた電極の過電圧は小さい。工業的に有
用な非水系二次電池電極を提供することができる。[Effects of the Invention] As shown in Table 1, the overvoltage of the electrode prepared by the coating solution of the present invention is small. It is possible to provide an industrially useful non-aqueous secondary battery electrode.

Claims (2)

【０００１】 【特許請求の範囲】[Claims] 【請求項１】 電池活物質を９８．５重量％〜８５重量
％とプロピレンと四フッ化エチレンとの共重合体、及び
又はプロピレンと四フッ化エチレンとフッ化ビニリデン
との共重合体のプロピレン−フッソ系共重合体類を０．
１重量％〜１３重量％とカルボキシメチルセルロース類
０．２重量％〜２重量％とポリアクリル酸類０重量％〜
１．０重量％を含んでなる水性分散体であることを特徴
とする電極用塗布ペースト。1. A copolymer of 98.5% by weight to 85% by weight of a battery active material and propylene and tetrafluoroethylene, and / or propylene which is a copolymer of propylene, tetrafluoroethylene and vinylidene fluoride. Fluorine-based copolymers of 0.
1% to 13% by weight, carboxymethylcelluloses 0.2% to 2% by weight, and polyacrylic acids 0% by weight
An electrode coating paste, which is an aqueous dispersion containing 1.0% by weight. 【請求項２】 電池活物質を９８．５重量％〜８５重量
％とプロピレンと四フッ化エチレンとの共重合体、及び
又はプロピレンと四フッ化エチレンとフッ化ビニリデン
との共重合体のプロピレン−フッソ系共重合体類を０．
１重量％〜１３重量％とカルボキシメチルセルロース類
０．２重量％〜２重量％とポリアクリル酸類０重量％〜
１．０重量％を含んでなることを特徴とする非水系二次
電池電極。 【０００２】2. A copolymer of 98.5% by weight to 85% by weight of a battery active material and propylene and tetrafluoroethylene, and / or propylene which is a copolymer of propylene, tetrafluoroethylene and vinylidene fluoride. Fluorine-based copolymers of 0.
1% to 13% by weight, carboxymethylcelluloses 0.2% to 2% by weight, and polyacrylic acids 0% by weight
A non-aqueous secondary battery electrode comprising 1.0% by weight. [0002]
JP8157339A 1996-05-14 1996-05-14 Applying paste for electrode and nonaqueous secondary battery electrode Pending JPH09306474A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8157339A JPH09306474A (en) 1996-05-14 1996-05-14 Applying paste for electrode and nonaqueous secondary battery electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8157339A JPH09306474A (en) 1996-05-14 1996-05-14 Applying paste for electrode and nonaqueous secondary battery electrode

Publications (1)

Publication Number Publication Date
JPH09306474A true JPH09306474A (en) 1997-11-28

Family

ID=15647534

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8157339A Pending JPH09306474A (en) 1996-05-14 1996-05-14 Applying paste for electrode and nonaqueous secondary battery electrode

Country Status (1)

Country Link
JP (1) JPH09306474A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002528863A (en) * 1998-10-20 2002-09-03 フラオンホッファー−ゲゼルシャフト ツーァ フェルデルング デーァ アンゲヴァンテン フォルシュング エー．ファオ． Paste material having inorganic liquid conductor, and layer and electrochemical element obtained therefrom
WO2004006363A1 (en) * 2002-07-05 2004-01-15 Daikin Industries, Ltd. Additive for electrode
WO2004097961A3 (en) * 2003-04-30 2005-07-07 Univ Montreal Polymeric binder for fused salts electrolytes based batteries
JP2006107767A (en) * 2004-09-30 2006-04-20 Dainippon Printing Co Ltd Coating composition for active substance layer, electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery
JP2009245921A (en) * 2008-03-13 2009-10-22 Denso Corp Electrode for secondary battery, method of manufacturing the same, and secondary battery employing the same
WO2012043763A1 (en) * 2010-09-30 2012-04-05 旭硝子株式会社 Electrode mixture for electricity-storage device, method for manufacturing said electrode mixture, and electricity-storage-device electrode and lithium-ion secondary battery using said electrode mixture
WO2012111770A1 (en) 2011-02-18 2012-08-23 旭硝子株式会社 Method for producing fluorine-containing copolymer latex, fluorine-containing copolymer latex, binder for electrode production, electrode mixture for electricity storage devices, and electrode for electricity storage devices
WO2013054743A1 (en) * 2011-10-14 2013-04-18 旭硝子株式会社 Lithium-ion rechargeable battery electrode, and method for producing same

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4970652B2 (en) * 1998-10-20 2012-07-11 ルクランシェ ソスィエテ アノニム Layer that can be applied to a substrate or self-supporting layer and method for producing the same, composite layer and method for producing the same, and method of using the layer and composite layer
JP2002528863A (en) * 1998-10-20 2002-09-03 フラオンホッファー−ゲゼルシャフト ツーァ フェルデルング デーァ アンゲヴァンテン フォルシュング エー．ファオ． Paste material having inorganic liquid conductor, and layer and electrochemical element obtained therefrom
WO2004006363A1 (en) * 2002-07-05 2004-01-15 Daikin Industries, Ltd. Additive for electrode
WO2004097961A3 (en) * 2003-04-30 2005-07-07 Univ Montreal Polymeric binder for fused salts electrolytes based batteries
JP2006524884A (en) * 2003-04-30 2006-11-02 ユニベルシテ ドゥ モントリオール Polymer binder for molten salt electrolyte battery
JP2006107767A (en) * 2004-09-30 2006-04-20 Dainippon Printing Co Ltd Coating composition for active substance layer, electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery
JP2009245921A (en) * 2008-03-13 2009-10-22 Denso Corp Electrode for secondary battery, method of manufacturing the same, and secondary battery employing the same
WO2012043763A1 (en) * 2010-09-30 2012-04-05 旭硝子株式会社 Electrode mixture for electricity-storage device, method for manufacturing said electrode mixture, and electricity-storage-device electrode and lithium-ion secondary battery using said electrode mixture
WO2012111770A1 (en) 2011-02-18 2012-08-23 旭硝子株式会社 Method for producing fluorine-containing copolymer latex, fluorine-containing copolymer latex, binder for electrode production, electrode mixture for electricity storage devices, and electrode for electricity storage devices
US9373845B2 (en) 2011-02-18 2016-06-21 Asahi Glass Company, Limited Method for producing fluorinated copolymer latex, fluorinated copolymer latex, binder for producing electrode, electrode mixture for storage battery device, and electrode for storage battery device
US9714336B2 (en) 2011-02-18 2017-07-25 Asahi Glass Company, Limited Method for producing fluorinated copolymer latex, fluorinated copolymer latex, binder for producing electrode, electrode mixture for storage battery device, and electrode for storage battery device
WO2013054743A1 (en) * 2011-10-14 2013-04-18 旭硝子株式会社 Lithium-ion rechargeable battery electrode, and method for producing same
JPWO2013054743A1 (en) * 2011-10-14 2015-03-30 旭硝子株式会社 Positive electrode for lithium ion secondary battery and method for producing the same

Similar Documents

Publication Publication Date Title
JP7020118B2 (en) Binder composition for non-aqueous secondary battery electrodes, slurry composition for non-aqueous secondary battery electrodes, electrodes for non-aqueous secondary batteries, and non-aqueous secondary batteries
US8426062B2 (en) Binder composition for nonaqueous electrolyte secondary battery electrode and nonaqueous electrolyte secondary battery
JP4259778B2 (en) Method for producing positive electrode for non-aqueous secondary battery
JP6519581B2 (en) Conductive adhesive composition for electrochemical element electrode and current collector for electrochemical element electrode
JP2971451B1 (en) Lithium secondary battery
WO2017056466A1 (en) Binder composition for nonaqueous secondary battery electrodes, slurry composition for nonaqueous secondary battery electrodes, electrode for nonaqueous secondary batteries, and nonaqueous secondary battery
EP3435456B1 (en) Binder composition for nonaqueous secondary battery electrodes, slurry composition for nonaqueous secondary battery electrodes, electrode for nonaqueous secondary batteries, and nonaqueous secondary battery
WO2014119790A1 (en) Slurry for lithium ion secondary battery positive electrodes
WO2013062088A1 (en) Conductive adhesive composition, collector with adhesive layer, and electrochemical element electrode
WO2013099990A1 (en) Positive electrode for secondary batteries, method for producing same, slurry composition, and secondary battery
WO2019156031A1 (en) Lithium ion secondary battery electrode, production method for same, and lithium ion secondary battery
JP6498300B2 (en) Electrodes for electrochemical devices
WO2016024383A1 (en) Binder composition for secondary battery electrodes, slurry composition for secondary battery electrodes, electrode for secondary battery, and secondary battery
US5714282A (en) Coating paste and a nonaqueous electrode for a secondary battery
WO2018155345A1 (en) Binder composition for nonaqueous secondary batteries, slurry composition for nonaqueous secondary battery functional layers, functional layer for nonaqueous secondary batteries, and nonaqueous secondary battery
JP6477691B2 (en) Secondary battery electrode binder composition, secondary battery electrode slurry composition, secondary battery electrode, and secondary battery
JP6696534B2 (en) Method for producing slurry for secondary battery positive electrode, method for producing positive electrode for secondary battery, and method for producing secondary battery
WO2015174036A1 (en) Binder composition for secondary battery electrodes, slurry composition for secondary battery electrodes, electrode for secondary batteries, production method therefor, and secondary battery
WO2018016528A1 (en) Electrode for lithium ion batteries, and lithium ion battery
JP3540097B2 (en) Electrode mixture for non-aqueous battery and non-aqueous battery
JPH09306474A (en) Applying paste for electrode and nonaqueous secondary battery electrode
JPH08321298A (en) Paste for applying to electrode and non-aqueous type secondary battery electrode
JP4654501B2 (en) Non-aqueous secondary battery
JPH06150906A (en) Nonaqueous secondary battery
JP2003017370A (en) Coating paste for capacitor and electric double layer capacitor electrode