JPS63121262A - Electrode for nonaqueous cell - Google Patents

Electrode for nonaqueous cell

Info

Publication number
JPS63121262A
JPS63121262A JP61266304A JP26630486A JPS63121262A JP S63121262 A JPS63121262 A JP S63121262A JP 61266304 A JP61266304 A JP 61266304A JP 26630486 A JP26630486 A JP 26630486A JP S63121262 A JPS63121262 A JP S63121262A
Authority
JP
Japan
Prior art keywords
electrode
binder
active material
battery
electrode active
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.)
Granted
Application number
JP61266304A
Other languages
Japanese (ja)
Other versions
JPH084007B2 (en
Inventor
Kenichi Sanechika
健一 実近
Akira Yoshino
彰 吉野
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.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
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 Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP61266304A priority Critical patent/JPH084007B2/en
Publication of JPS63121262A publication Critical patent/JPS63121262A/en
Publication of JPH084007B2 publication Critical patent/JPH084007B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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

Abstract

PURPOSE:To improve cell performance by constituting a binder with mainly specific monomer units. CONSTITUTION:A fluorine macromolecule copolymer constituted of mainly monomer units A, B, C shown by Formula I is used as a binder, and ratios XA, XB, XC between the monomer units A, B, C are set to 0.3<=xA<=0.9, 0.03<=XB<=0.5, 0<=XC<=0.5, 0.80<=XA+XB+XC<= 1, preferably 0.4<=XA<=0.8, 0.1<=XB<=0.3, 0.1<=XC<=0.4. The quantity of the binder used is 0.1-20 pts.wt., preferably 0.5-10 pts.wt., against the electrode active material 100 pts.wt., for example. Thereby, problems on production processes, e.g., problems on drying, toxicity of solvent, recovery of solvent, chemical resistance of coating installation, etc., can be dissolved, and an electrode having excellent performance can be obtained at a low cost.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は新規な非水系電池電極に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel non-aqueous battery electrode.

［従来の技術］ 近年、電子機器の小型化、軽量化は目覚まし□く、それ
に伴い電源となる電池に対しても小型軽量化の要望が非
常に大きい、かかる要求を満足するには従来の一般的な
水系電解液を用いた電池では不可能なことから、非水系
電池が注目されている。かかる非水系電池は小型、軽量
化という点で優れた性能を有しており、リチウム電池に
代表される一次電池、更にはリチウム／二硫化チタン二
次電池等が提案されており、その一部については既に実
用化されている。[Prior Art] In recent years, electronic devices have become increasingly smaller and lighter.As a result, there is a great demand for batteries that serve as power sources to be smaller and lighter.In order to satisfy these demands, conventional general Non-aqueous batteries are attracting attention because this is not possible with batteries using standard aqueous electrolytes. Such non-aqueous batteries have excellent performance in terms of being small and lightweight, and primary batteries such as lithium batteries, as well as lithium/titanium disulfide secondary batteries, etc., have been proposed. has already been put into practical use.

しかしながら、かかる非水系電池は高エネルギー密度、
小型軽量といった性能面では優れているものの、水系電
池に比べ出力特性に難点があり、広く一般に用いられる
までに至っていない。特に出力特性が要求される二次電
池の分野ではこの欠点が実用化を妨げている一つの要因
となっている。非水系電池が出力特性に劣る原因は水系
電解液の場合イオン電導度が高く、通常１０−１Ω−Ｉ
　Ｃｌｍ−１オーダーの値を有するのに対し、非水系の
場合通常１０−２〜１Ｏ−４Ω−＋Ｈ−＋と低いイオン
電導度しか有していないことに起因する。However, such non-aqueous batteries have high energy density,
Although they are superior in terms of performance such as small size and light weight, they have disadvantages in output characteristics compared to water-based batteries, so they have not been widely used. Particularly in the field of secondary batteries, where output characteristics are required, this drawback is one of the factors preventing practical use. The reason why nonaqueous batteries have inferior output characteristics is that aqueous electrolytes have high ionic conductivity, usually 10-1Ω-I.
This is due to the fact that non-aqueous systems usually have a low ionic conductivity of 10-2 to 10-4 Ω-+H-+, whereas they have a value on the order of Clm-1.

かかる問題点を解決する一つの方法として電極面積を大
きくすること、即ち薄膜、大面積電極を用いることが考
えられる。One possible way to solve this problem is to increase the area of the electrode, that is, to use a thin film or a large-area electrode.

従来、電極の成形方法としては、電極活物質をテフロン
粉末、ポリエチレン粉末等の粉末状バインダーと共に混
合し圧縮成形する方法が一般的である。かかる方法の場
合、絶縁性物質であるバインダーの電極活物質に対する
影響が比較的少ないという利点がある反面、薄膜、大面
積の電極を製造することは極めて困難であり、本発明の
意図とする高出力型非水系電池を得ることはできない。Conventionally, a common method for forming electrodes is to mix an electrode active material with a powdered binder such as Teflon powder or polyethylene powder, and then compression mold the mixture. Although such a method has the advantage that the binder, which is an insulating material, has relatively little influence on the electrode active material, it is extremely difficult to manufacture a thin film and a large-area electrode, and it is difficult to manufacture a thin film and a large-area electrode. It is not possible to obtain a power type non-aqueous battery.

一方、ブタジェンゴム等の有機溶剤溶液やスチレン／ブ
タジェンゴム等の水乳化分散液等に電極活物質を分散し
た後、塗工乾燥することにより電極を成形する方法も知
られている。この方法によればｇ膜、大面積の電極が容
易に得られ非常に好都合である反面、絶縁性物質である
バインダーの電極活物質に対する影響が著しく大きく、
該電極を電池に組立てた場合、例えば著しい過電圧の上
昇が見られ実用的な方法ではなかった。On the other hand, a method is also known in which an electrode is formed by dispersing an electrode active material in an organic solvent solution such as butadiene rubber or a water emulsion dispersion such as styrene/butadiene rubber, followed by coating and drying. Although this method is very advantageous in that it is easy to obtain a G film and a large-area electrode, it has a significant effect on the electrode active material of the binder, which is an insulating material.
When this electrode was assembled into a battery, for example, a significant increase in overvoltage was observed, and this was not a practical method.

かかる問題点を解決する提案として、特開昭８１−７５
８８において、７ツ化ビニル、フッ化ビニリデン等のフ
ッ素系高分子は陽イオンをドーパントとし得る活物質に
対して優れたバインダーとなることが開示されている。As a proposal to solve such problems,
No. 88 discloses that fluorine-based polymers such as vinyl heptadide and vinylidene fluoride serve as excellent binders for active materials in which cations can be used as dopants.

特に、活物質としてポリフェニレン、ポリアセチレンま
たはフタロシアニン類を用いた場合、該バインダーは債
れた性能を示し、放電容量の向上という好ましい結果を
もたらしている。In particular, when polyphenylene, polyacetylene or phthalocyanine is used as the active material, the binder exhibits excellent performance and brings about favorable results such as improved discharge capacity.

前述の如く、該フッ素系高分子であるフッ化ビニル、フ
ッ化ビニリデン等はバインダーとして優れた性能を示す
がその反面、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、テトラメチル尿素等の特殊な溶剤にしか溶けないと
いう問題点を有している。該溶剤は沸点が高く、極性の
強い溶剤であって中には毒性のあるものも含まれている
。故に工業的観点より、該溶剤を用いて活物質を塗布成
形し電極を製造する場合、以下に示す問題が発生する。As mentioned above, the fluorine-based polymers such as vinyl fluoride and vinylidene fluoride exhibit excellent performance as binders, but on the other hand, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoamide, dimethylsulfoxide, and tetramethylurea The problem is that it only dissolves in special solvents such as These solvents have high boiling points and strong polarity, and some of them are toxic. Therefore, from an industrial standpoint, when an electrode is manufactured by applying and molding an active material using the solvent, the following problems occur.

１）沸点が高いため塗布後の乾燥工程が大変である。２
）毒性があるので、密閉設備、排気設備等を整備する必
要がある。３）コストが高いので溶剤の回収設備の必要
性が生じる。1) Due to the high boiling point, the drying process after application is difficult. 2
) Since it is toxic, it is necessary to provide sealing equipment, exhaust equipment, etc. 3) High cost creates the need for solvent recovery equipment.

４）極性が強いので塗工設備の耐薬品性に留意しなけれ
ばならない。4) Due to its strong polarity, care must be taken to ensure the chemical resistance of coating equipment.

［発明が解決しようとする問題点］ 前述の如く、フッ化ビニル、フッ化ビニリデン等のフッ
素重合体をバインダーとして用いた電極の塗布成形法は
、実用的な製造プロセスと言う観点からは未だ問題が解
決されていないのが現状である。[Problems to be Solved by the Invention] As mentioned above, the coating molding method of electrodes using fluoropolymers such as vinyl fluoride and vinylidene fluoride as binders still has problems from the viewpoint of a practical manufacturing process. The current situation is that the issue has not been resolved.

［問題点を解決するための手段及び作用］本発明は前述
の問題点を解決し、工業的塗工プロセスにおいて容易に
電極が製造され、その結果として優れた電池性能を有す
る非水系電池用電極が提供されるためになされたもので
ある。[Means and effects for solving the problems] The present invention solves the above-mentioned problems, and provides an electrode for non-aqueous batteries that can be easily manufactured in an industrial coating process and has excellent battery performance as a result. This was done in order to provide the following.

本発明によれば、バインダーと電極活物質からなる非水
系電池電極であって、該バインダーが下記に示すモノマ
ーユニットＡ、Ｂ、Ｃより主として構成されるフッ素系
高分子共重合体であって。According to the present invention, there is provided a nonaqueous battery electrode comprising a binder and an electrode active material, wherein the binder is a fluoropolymer copolymer mainly comprised of monomer units A, B, and C shown below.

各モノマーユニットのモル分率がＸＡｔ　Ｘ８．　ｘｃ
が０．３　≦Ｘｘ≦０．９．０．０３　≦ＸＢ≦０．５
．０　≦ＸＣ≦０．５゜０．８０≦ＸＡ十Ｘ８＋ＸＣ≦
１の範囲にあることを特徴とする非水系電池用電極が提
供される。The mole fraction of each monomer unit is XAt X8. xc
is 0.3 ≦Xx≦0.9.0.03 ≦XB≦0.5
．． 0 ≦XC≦0.5゜0.80≦XA×8+XC≦
Provided is an electrode for a non-aqueous battery that is characterized by being in the range of 1.

Ａ　　　−Ｃ１ｈ−ＣＦｚ− Ｂ−ＣＦ−ＣＦ２− ？ ＣＦ３ Ｃ−ＣＦ２−ＣＦｚ− 前述の如く、溶媒に溶解及び／又は分散した有機重合体
をバインダーとして電極活物質を成形した場合、電池特
性として好ましくない現象が見出される。その理由は定
かではないが、恐らく電極活物質の表面が絶縁性のバイ
ンダー有機重合体により覆われ、円滑なイオンの拡散が
妨げられる為だと思われる。A -C1h-CFz- B-CF-CF2-? CF3 C-CF2-CFz- As described above, when an electrode active material is formed using an organic polymer dissolved and/or dispersed in a solvent as a binder, unfavorable phenomena regarding battery characteristics are found. The reason for this is not clear, but it is probably because the surface of the electrode active material is covered with an insulating binder organic polymer, which prevents smooth ion diffusion.

かかる問題点を解決するため、７ツ化ビニル・フッ化ビ
ニリデン等のフッ素系高分子をバインダーとして用いる
ことが提案され、該フッ素系高分子が優れたバインダー
であることが示されたが、該フッ素系高分子は特殊な溶
剤にしか溶けないため、実用上例えば設備、毒性、コス
トの面で多くの問題点を有していることが判明した。In order to solve these problems, it has been proposed to use fluoropolymers such as vinyl heptadide and vinylidene fluoride as binders, and it has been shown that these fluoropolymers are excellent binders. Since fluoropolymers are soluble only in special solvents, it has been found that they have many practical problems in terms of equipment, toxicity, and cost, for example.

本発明者らは、特定のバインダー即ち前述のモノマーユ
ニー、）Ａ、Ｂ、Ｃより主として構成されるフッ素系高
分子共重合体をバインダーとして用いた場合、この様な
実用上の問題点が全く生じないことを見出した０本発明
で言う該フッ素系高分子共重合体とは、前述の千ツマー
ユニットＡ　、　Ｂ　、　Ｃ（７）割合ｘＡｎ　ｘａ、
　ｘｃが０．３　≦Ｘａ≦０．９．０．０３≦ＸＢ≦０
．５．０≦ＸＣ≦０．５゜０．８０≦ＸＡ＋Ｘａ＋ＸＣ
≦１　テＴｏ　ル、好ｔ　Ｌ　＜　４ｉ　。The present inventors have discovered that when a specific binder, that is, a fluoropolymer copolymer mainly composed of the monomer units A, B, and C described above, is used as a binder, such practical problems are completely eliminated. The fluorine-based polymer copolymer referred to in the present invention means the above-mentioned 1,000 units A, B, C (7) ratio x An xa,
xc is 0.3 ≦Xa≦0.9.0.03≦XB≦0
．． 5.0≦XC≦0.5゜0.80≦XA+Xa+XC
≦1T, L<4i.

０．４　≦Ｘａ≦０．８．０．１≦ＸＢ≦０．３．０．
１’≦ＸＣ≦０．４　テある高分子共重合体のことを言
い、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、このバインダー溶液を用いて製膜した電極は
優れた性能を示した。　ＸＡが０．３より小さい場合は
、フッ素系高分子独特の特性に基づくと思われる電気的
性質が損われ、電極性能が低下した。ｘＡが０．９より
大きい場合、Ｘ８が０．５より大きい場合。0.4≦Xa≦0.8.0.1≦XB≦0.3.0.
1' ≦ demonstrated its performance. When XA was smaller than 0.3, the electrical properties, which are thought to be based on the unique characteristics of fluoropolymer, were impaired, and the electrode performance was degraded. When xA is greater than 0.9, when X8 is greater than 0.5.

ＸＣが０．５より大きい場合においては通常の溶剤に対
する溶解性が著しく乏しくなり、バインダー溶液をｇＪ
整することができなかったａＸＢが０，０３より小さい
場合は、製膜体が脆く、電極性能においてあまり好まし
い結果を与えなかった。該フッ素系高分子共重合体にお
いて七ツマーユニットＡ。When XC is larger than 0.5, the solubility in ordinary solvents becomes extremely poor, and the binder solution is
When aXB, which could not be adjusted, was smaller than 0.03, the film formed body was brittle and did not give very favorable results in terms of electrode performance. Seven mer units A in the fluorine-based polymer copolymer.

Ｂ、Ｃ以外の成分、例えばプロピレン等が組込まレテモ
良イカ、　ソ（７）範囲４ｆ０．８０≦Ｘａ＋Ｘｅ＋Ｘ
Ｃ≦１が好ましい。Ingredients other than B and C, such as propylene, are incorporated, so (7) Range 4f0.80≦Xa+Xe+X
C≦1 is preferred.

本発明範囲のフッ素系高分子は、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。バインダー溶
液溶剤としては、例えば、メチルエチルケトン、メチル
イソブチルケトン等のケトン系溶剤、エチルアセテート
、ブチルアセテート等のエステル系溶剤、ジオキサン、
シクロヘキサノン等のエーテル系溶剤さらにはそれらの
混合溶剤をあげることができる。The fluoropolymer within the scope of the present invention is easily dissolved in common coating solvents and provides a stable binder solution. Examples of binder solution solvents include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, dioxane,
Examples include ether solvents such as cyclohexanone, and mixed solvents thereof.

かかるフッ素系高分子をバインダーとして用いるに際し
ては、該フッ素系高分子を溶媒に溶解せしめたバインダ
ー溶液に電極活物質を分散せしめたものを塗工液として
用いる方法、予め予備成形された電極活物質に該フッ素
系高分子の溶液及び／又は分散液を塗布する方法等が一
例として挙げられる。用いるバインダー量は特に限定す
るものではないが、通常、電極活物質１００重量部に対
して０．１〜２０重量部、好ましくは０．５〜ｌＯ重量
部の範囲である。When using such a fluoropolymer as a binder, there are methods in which an electrode active material is dispersed in a binder solution in which the fluoropolymer is dissolved in a solvent, and a coating solution is used, or a preformed electrode active material is used. An example is a method of applying a solution and/or dispersion of the fluoropolymer to the fluoropolymer. The amount of the binder used is not particularly limited, but is usually in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the electrode active material.

本発明のフッ素系高分子をバインダーとして用いれば、
前述の如〈従来問題とされていた製造プロセス上の問題
、例えば１）乾燥が大変である。If the fluoropolymer of the present invention is used as a binder,
As mentioned above, there are conventional manufacturing process problems such as: 1) Drying is difficult.

２）溶剤の毒性３）溶剤の回収０塗工設備の耐薬品性等
にかかわる問題を解決することができ、優れた性能を有
する電極を安価に提供することが可能である。2) Solvent toxicity 3) No solvent recovery Problems related to chemical resistance of coating equipment can be solved, and electrodes with excellent performance can be provided at low cost.

本発明で用いられる電極活物質は特に限定されるもので
はないが、−例を示せば１口０２　、　ＭｏＯ３。The electrode active material used in the present invention is not particularly limited, but examples include MoO2 and MoO3.

Ｖ２Ｏ５，Ｖ６Ｏ１３，Ｆｅ２Ｏ３，Ｆｅ５０＊、　Ｌ
ｉ（＋−ｘ）ｃｏ０２＋Ｌｉｕ−ｘ）・旧０２．　Ｔｉ
Ｓ２．〒ｉＳ３．　ＭＯ５３，Ｆｌ！Ｓ２．　ＣｕＦ２
゜Ｎ　ｉＦ２等の無機化合物、フッ化カーボン、グラフ
ァイト、気相成長炭素繊維及び／又はその粉砕物、ＰＡ
Ｎ系炭素炭素繊維／又はその粉砕物、ピッチ系炭素繊維
及び／又はその粉砕物等の炭素材料、ポリアセチレン、
ポリ−ｐ−フェニレン等の導電性高分子等が挙げられる
。V2O5, V6O13, Fe2O3, Fe50*, L
i(+-x)co02+Liu-x)・Old 02. Ti
S2. 〒iS3. MO53, Fl! S2. CuF2
゜Inorganic compounds such as N iF2, carbon fluoride, graphite, vapor-grown carbon fibers and/or pulverized products thereof, PA
Carbon materials such as N-based carbon fibers/or pulverized products thereof, pitch-based carbon fibers and/or pulverized products thereof, polyacetylene,
Examples include conductive polymers such as poly-p-phenylene.

該電極活物質が粉末状の場合には、バインダー液と混合
した後、大村上に塗布乾燥することにより成形される。When the electrode active material is in powder form, it is molded by mixing it with a binder liquid and then coating it on Omura and drying it.

この時要すれば集電体材料と共に成形しても良いし、又
、別法としてアルミ箔、銅箔等の集電体を基材として用
いることもできる。At this time, if necessary, it may be molded together with the current collector material, or alternatively, a current collector such as aluminum foil or copper foil may be used as the base material.

又、電極活物質が繊維状の場合には予めシート状、リボ
ン状等の形状に整えた後、バインダー液を塗布乾燥する
ことにより成形する方法も考えられる。In addition, when the electrode active material is in the form of fibers, it is also possible to form the material into a sheet, ribbon, etc. shape in advance, and then apply a binder liquid thereon and dry it.

本発明の非水系電池電極は用いる電極活物質により、正
極として用いても良いし、負極として用いても良い０本
発明の非水系電池電極を用い電池を組立てる場合、非水
電解液の電解質としては特に限定されないが、−例を示
せば、　Ｌ：Ｃβ０４゜ＬｉＢＦＪ、　ＬｉＡｓＦ６．
　ＣＦ３ＳＯ３Ｌｉ、　ＬｉＰＦ６．ＬｉＩ。The non-aqueous battery electrode of the present invention may be used as a positive electrode or a negative electrode depending on the electrode active material used. When assembling a battery using the non-aqueous battery electrode of the present invention, it may be used as an electrolyte of a non-aqueous electrolyte. is not particularly limited, but examples include: L:Cβ04°LiBFJ, LiAsF6.
CF3SO3Li, LiPF6. LiI.

ＬｉＡｊＩＣｊ’ａ、　Ｎａ１Ｊ）Ｏｎ、　ＮａＢＦａ
、　ＮａＩ、　（ｎ−Ｂｕ）４Ｎ１″ｃｊ！０４゜（ｎ
−Ｂｕ）ａＮ＠ＢＦ４．　ＫＰＦ６等が挙げられる。又
、用いられる電解液の有機溶媒としては、例えばエーテ
ル類、ケトン類、ラクトン類、ニトリル類、アミン類、
アミド類、硫黄化合物、塩素化炭化水素類、エステル類
、カーボネート類、ニトロ化合物、リン酸エステル系化
合物、スルホラン系化合物等を用いることができるが、
これらのうちでもエーテル類、ケトン類、ニトリル類、
塩素化炭化水素類、カーボネート類、スルホラン系化合
物が好ましい。LiAjICj'a, Na1J)On, NaBFa
, NaI, (n-Bu)4N1″cj!04゜(n
-Bu)aN@BF4. Examples include KPF6. In addition, examples of organic solvents used in the electrolytic solution include ethers, ketones, lactones, nitriles, amines,
Amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, phosphate ester compounds, sulfolane compounds, etc. can be used, but
Among these, ethers, ketones, nitriles,
Chlorinated hydrocarbons, carbonates, and sulfolane compounds are preferred.

これらの代表例としては、テトラヒドロフラン、２−メ
チルテトラヒドロフラン、１，４−ジオキサン、アニソ
ール、モノグライム、アセトニトリル。Representative examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, anisole, monoglyme, and acetonitrile.

プロピオニトリル、４−メチル−２−ペンタノン。Propionitrile, 4-methyl-2-pentanone.

ブチロニトリル、バレロニトリル、ベンゾニトリル、１
．２−ジクロロエタン、γ−ブチロラクトン、ジメトキ
シエタン、メチルフォルメイト、プロピレンカーボネー
ト、エチレンカーボネート、ジメチルホルムアミド、ジ
メチルスルホキシド、ジメチルチオホルムアミド、スル
ホラン、３−メチル−スルホラン、リン酸トリメチル、
リン酸トリエチルおよびこれらの混合溶媒等をあげるこ
とができるが、必ずしもこれらに限定されるものではな
い。Butyronitrile, Valeronitrile, Benzonitrile, 1
．． 2-dichloroethane, γ-butyrolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate,
Examples include triethyl phosphate and mixed solvents thereof, but are not necessarily limited thereto.

更に、要すればセパレーター、集電体、端子、絶縁板等
の部品を用いて電池が構成される。又。Furthermore, if necessary, the battery is constructed using parts such as a separator, a current collector, a terminal, and an insulating plate. or.

電池の構造としては、特に限定されるものではないが、
正極、負極、更に要すればセパレーターを単層又は複層
としたペーパー型電池、又は正極、負極、更に要すれば
セパレーターをロール状に巻いた円筒状電池等の形態が
一例として挙げられる。Although the structure of the battery is not particularly limited,
Examples include a paper type battery having a positive electrode, a negative electrode, and, if necessary, a separator in a single layer or a multilayer, or a cylindrical battery having a positive electrode, a negative electrode, and, if necessary, a separator wound into a roll.

［実施例］ 以下、実施例、比較例により本発明を更に詳しく説明す
る。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

実施例１ 平均粒径２ｇｍのＬｉ＋、ｏ３Ｃｏｏ、ｑｓＳｎｏ、ｏ
４２０２４２０重量部に対し、平均粒径５μ腸のグラフ
ァイト０．０７５重量部と平均粒径０．０３６ｍのアセ
チレンブラックを０．０２５重量部を混ぜ、さらに各ユ
ニー／　トの割合がＸＡ＝　０．５８．　Ｘａ＝　０．
２４．　ＸＣ＝　０．１８テあるフッ素系共重合体のメ
チルイソブチルケトン溶液（Ｂ度４ｗｔ％）を０．５重
量部加え、混合攪拌し塗工液とした。市販アルミ箔（厚
さ１５ｇ）を基材としてこの塗工液を片面に塗布乾燥し
、１００棒腸の膜厚を有する電極を得た。この電極製膜
体から１　ｃ＋ａＸ　５　ａｍを切り出し正極とした。Example 1 Li+, o3Coo, qsSno, o with an average particle size of 2 gm
4202420 parts by weight, 0.075 parts by weight of graphite with an average particle size of 5 μm and 0.025 parts by weight of acetylene black with an average particle size of 0.036 m were mixed, and the ratio of each unit was XA = 0.58. ．． Xa=0.
24. 0.5 parts by weight of a methyl isobutyl ketone solution (B degree 4 wt %) of a fluorine-based copolymer with XC = 0.18 was added and mixed and stirred to obtain a coating liquid. This coating solution was applied to one side of a commercially available aluminum foil (thickness 15 g) as a base material and dried to obtain an electrode having a film thickness of 100 rods. 1 c+aX 5 am was cut out from this electrode film body and used as a positive electrode.

市販の石油系ニードルコークス（興亜石油社製ＫＯＡ−
ＳＪ　Ｃａｋｅ）をボールミルで平均粒径１０ｇｍに粉
砕し、この粉砕物１重量部に対し、上記のフッ素系共重
合体のメチルイソブチルケトン溶液（濃度５ｗｔ％）を
１，０重量部加え、混合攪拌し塗工液とした。重版銅箔
（厚さ１０Ｉ＆＋ｓ）を基材としてこの塗工液を塗布乾
燥し、θＯＩＬｍの膜厚を有する電極を得た。この電極
製膜体からＩＣ層Ｘ５ｃｍを切り出し負極とした。電解
液として０．８　Ｍ　ＬｒＣＲＯａ　プロピレンカーボ
ネートを用い第１図に示す電池を組立てた。この電池の
１０ｍＡ　（電流密度２　ｍＡ／ｃｍ２）での充電放電
における過電圧は第１表に示す通りであった。Commercially available petroleum needle coke (KOA Oil Co., Ltd.)
SJ Cake) was ground to an average particle size of 10 gm using a ball mill, and to 1 part by weight of this ground product, 1.0 parts by weight of the above fluorine-based copolymer solution in methyl isobutyl ketone (concentration 5 wt%) was added, mixed and stirred. It was used as a coating liquid. This coating liquid was applied and dried using a reprinted copper foil (thickness 10I&+s) as a base material to obtain an electrode having a film thickness of θOILm. An IC layer x5 cm was cut out from this electrode film body and used as a negative electrode. The battery shown in FIG. 1 was assembled using 0.8 M LrCROa propylene carbonate as the electrolyte. The overvoltage of this battery during charging and discharging at 10 mA (current density 2 mA/cm2) was as shown in Table 1.

実施例２〜５　比較例１〜４ バインダーを第１表に示すものに代えた以外は実施例１
と同様な操作を行い、得られた電極については同様の評
価を行なった。その結果を第１表に示す。Examples 2 to 5 Comparative Examples 1 to 4 Example 1 except that the binder was replaced with one shown in Table 1.
The same operations as above were performed, and the obtained electrodes were evaluated in the same manner. The results are shown in Table 1.

但し、３，４に関しては、メチルエチルケトン、メチル
イソブチルケトン、アセトン、ブチルアセテート、ＩＩ
ＭＦ　、　Ｎ−メチルピロリドン、ジメチルアセトアミ
ド等の溶剤に不溶なためバインダー溶液を調製すること
ができない。However, regarding 3 and 4, methyl ethyl ketone, methyl isobutyl ketone, acetone, butyl acetate, II
Since it is insoluble in solvents such as MF, N-methylpyrrolidone, and dimethylacetamide, a binder solution cannot be prepared.

（以　下　余　白２(Below, remainder white 2

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の実施例、比較例で用いた電池の断面図
を示す。 １・・・正極及び電解液、　　２・・・負極及び電解液
、３・・・アルミ箔、　　　　　４・・・銅箔、５．５
ａ・・・集電棒、 ６・・・セパレーター及び電解液、 ７・・・電池ケース。FIG. 1 shows a cross-sectional view of a battery used in Examples and Comparative Examples of the present invention. 1... Positive electrode and electrolyte, 2... Negative electrode and electrolyte, 3... Aluminum foil, 4... Copper foil, 5.5
a... Current collector rod, 6... Separator and electrolyte, 7... Battery case.

Claims (1)

【特許請求の範囲】 バインダーと電極活物質からなる非水系電 池電極であって、該バインダーが下記に示すモノマーユ
ニットＡ、Ｂ、Ｃより主として構成されるフッ素系高分
子共重合体であって、各モノマーユニットのモル分率が
Ｘ＿Ａ、Ｘ＿Ｂ、Ｘ＿Ｃが０．３≦Ｘ＿Ａ≦０．９、０
．０３≦Ｘ＿Ｂ≦０．５、０≦Ｘ＿Ｃ≦０．５、０．８
０≦Ｘ＿Ａ＋Ｘ＿Ｂ＋Ｘ＿Ｃ≦１の範囲にあることを特
徴とする非水系電池用電極。 Ａ　−ＣＨ＿２−ＣＦ＿２− Ｂ　▲数式、化学式、表等があります▼ Ｃ　−ＣＦ＿２−ＣＦ＿２−[Scope of Claims] A non-aqueous battery electrode consisting of a binder and an electrode active material, the binder being a fluoropolymer copolymer mainly composed of monomer units A, B, and C shown below, The molar fraction of each monomer unit is X_A, X_B, X_C is 0.3≦X_A≦0.9, 0
．． 03≦X_B≦0.5, 0≦X_C≦0.5, 0.8
An electrode for a non-aqueous battery, characterized in that the electrode is in the range of 0≦X_A+X_B+X_C≦1. A -CH_2-CF_2- B ▲There are mathematical formulas, chemical formulas, tables, etc.▼ C -CF_2-CF_2-
JP61266304A 1986-11-08 1986-11-08 Electrode for non-aqueous battery Expired - Lifetime JPH084007B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61266304A JPH084007B2 (en) 1986-11-08 1986-11-08 Electrode for non-aqueous battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61266304A JPH084007B2 (en) 1986-11-08 1986-11-08 Electrode for non-aqueous battery

Publications (2)

Publication Number Publication Date
JPS63121262A true JPS63121262A (en) 1988-05-25
JPH084007B2 JPH084007B2 (en) 1996-01-17

Family

ID=17429071

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61266304A Expired - Lifetime JPH084007B2 (en) 1986-11-08 1986-11-08 Electrode for non-aqueous battery

Country Status (1)

Country Link
JP (1) JPH084007B2 (en)

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Publication number Priority date Publication date Assignee Title
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
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CN1057874C (en) * 1991-09-13 2000-10-25 旭化成工业株式会社 Secondary battery
WO2011002097A1 (en) * 2009-07-03 2011-01-06 ダイキン工業株式会社 Slurry for electrode mixture of lithium secondary cell, electrode using the slurry, and lithium secondary cell
WO2012115180A1 (en) * 2011-02-25 2012-08-30 クロリンエンジニアズ株式会社 Anode catalyst and manufacturing method therefor
CN104285320A (en) * 2012-05-21 2015-01-14 大金工业株式会社 Electrode mixture
CN104350635A (en) * 2012-05-21 2015-02-11 大金工业株式会社 Electrode mixture
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EP0964464B1 (en) * 1996-12-16 2010-08-25 Daikin Industries, Ltd. Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same
US9257696B2 (en) 2009-02-12 2016-02-09 Daikin Industries, Ltd. Positive electrode mixture slurry for lithium secondary batteries, and positive electrode and lithium secondary battery that use said slurry

Cited By (13)

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Publication number Priority date Publication date Assignee Title
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
CN1057874C (en) * 1991-09-13 2000-10-25 旭化成工业株式会社 Secondary battery
JPH0831408A (en) * 1994-05-13 1996-02-02 Matsushita Electric Ind Co Ltd Positive electrode for non-aqueous electrolyte lithium secondary battery and manufacture thereof
JPH10162832A (en) * 1996-11-27 1998-06-19 Yuasa Corp Thin lithium battery, and manufacture thereof
JP5382120B2 (en) * 2009-07-03 2014-01-08 ダイキン工業株式会社 Slurry for electrode mixture of lithium secondary battery, electrode using the slurry, and lithium secondary battery
WO2011002097A1 (en) * 2009-07-03 2011-01-06 ダイキン工業株式会社 Slurry for electrode mixture of lithium secondary cell, electrode using the slurry, and lithium secondary cell
WO2012115180A1 (en) * 2011-02-25 2012-08-30 クロリンエンジニアズ株式会社 Anode catalyst and manufacturing method therefor
JP5873071B2 (en) * 2011-02-25 2016-03-01 デノラ・ペルメレック株式会社 Method for producing anode catalyst body and method for producing electrolytic cell for ozone generation
CN104285320A (en) * 2012-05-21 2015-01-14 大金工业株式会社 Electrode mixture
CN104350635A (en) * 2012-05-21 2015-02-11 大金工业株式会社 Electrode mixture
US9444104B2 (en) 2012-05-21 2016-09-13 Daikin Industries, Ltd. Electrode mixture
US9444103B2 (en) 2012-05-21 2016-09-13 Daikin Industries, Ltd. Electrode mixture
JP2016025025A (en) * 2014-07-23 2016-02-08 トヨタ自動車株式会社 Method for manufacturing negative electrode for solid battery, method for manufacturing solid battery, and slurry for negative electrode

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