JP2000133269A - Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery - Google Patents

Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery

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Publication number
JP2000133269A
JP2000133269A JP10307048A JP30704898A JP2000133269A JP 2000133269 A JP2000133269 A JP 2000133269A JP 10307048 A JP10307048 A JP 10307048A JP 30704898 A JP30704898 A JP 30704898A JP 2000133269 A JP2000133269 A JP 2000133269A
Authority
JP
Japan
Prior art keywords
secondary battery
electrode
active material
conductive
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.)
Pending
Application number
JP10307048A
Other languages
Japanese (ja)
Inventor
Takashi Watanabe
貴志 渡邉
Hiroyuki Nakatani
博之 中谷
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.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical 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 Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP10307048A priority Critical patent/JP2000133269A/en
Publication of JP2000133269A publication Critical patent/JP2000133269A/en
Pending legal-status Critical Current

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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

Abstract

PROBLEM TO BE SOLVED: To provide an electrode conductive auxiliary used for a nonaqueous secondary battery, particularly a nonaqueous lithium secondary battery, and having high ionic conductivity, electronic conductivity and a binding capability and to provide an electrode for the secondary battery using it and the secondary battery. SOLUTION: An electrode conductive auxiliary for a secondary battery made of a compound expressed by the formula and an electrode for the secondary battery formed with a film containing the conductive auxiliary and an electrode active material on a current collector are used for a positive electrode or a negative electrode, where R is the monovalent ionic conductivity organic group having the cyclic unit of 1-20, X indicates NH, S, O or Se, and (n) indicates an integer of 1-10,000.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は二次電池、特に非水
系のリチウム二次電池等に使用できる、高いイオン伝導
性及び電子伝導性と共にバインダーとしての結着能を併
せ持った二次電池の電極用導電助剤、二次電池の電極及
び二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for a secondary battery having high ionic conductivity and electron conductivity and binding ability as a binder, which can be used for a secondary battery, especially a non-aqueous lithium secondary battery. The present invention relates to a conductive assistant for use, an electrode of a secondary battery, and a secondary battery.

【０００２】[0002]

【従来の技術】二次電池、特にリチウムイオンを用いた
二次電池の電極は、正極の活物質として、主にＬｉＣｏ
Ｏ2 やＬｉＮｉＯ2 等の複合酸化物が用いられ、負極の
活物質として、主にカーボン粉末や異方性ピッチを焼成
した炭素化合物、高分子繊維、芳香族化合物等が用いら
れている。2. Description of the Related Art Electrodes of a secondary battery, particularly a secondary battery using lithium ions, mainly use LiCo as an active material of a positive electrode.
Composite oxides such as O2 and LiNiO2 are used, and as a negative electrode active material, carbon powder, a carbon compound obtained by firing an anisotropic pitch, a polymer fiber, an aromatic compound, and the like are mainly used.

【０００３】電極を製造する方法としては、電極活物質
を結着剤（バインダー樹脂とも称される) 及び溶剤と共
に混合してペーストを作成し、集電体である金属泊に塗
着、乾燥する手法が一般的に用いられている。As a method of manufacturing an electrode, a paste is prepared by mixing an electrode active material with a binder (also referred to as a binder resin) and a solvent, and the paste is applied to a metal foil as a current collector and dried. The technique is commonly used.

【０００４】例えば特開平６−２１５７６１号公報に
は、銅箔の両面に、負極活物質としての黒鉛粉末に、ポ
リ四フッ化エチレン分散液及びスチレン−ブタジエンゴ
ム分散液等のバインダー樹脂に分散させてペースト状に
したものを塗着して負極の電極板とし、一方、金属箔の
両面に、正極活物質としてのＬｉＣｏＯ2 をポリ四フッ
化エチレン分散液等のバインダー樹脂に分散させてペー
スト状にしたものを塗着して正極の電極板とした、非水
電解液系リチウム二次電池が開示されている。[0004] For example, Japanese Patent Application Laid-Open No. Hei 6-215762 discloses that copper powder is dispersed on both sides of a copper foil in a binder resin such as a polytetrafluoroethylene dispersion and a styrene-butadiene rubber dispersion on a graphite powder as a negative electrode active material. The negative electrode plate is applied by coating the paste into a paste, and LiCoO2 as a positive electrode active material is dispersed in a binder resin such as polytetrafluoroethylene dispersion on both surfaces of the metal foil to form a paste. A non-aqueous electrolyte-based lithium secondary battery is disclosed, in which the resultant is applied as a positive electrode plate.

【０００５】しかし、上記従来のリチウム二次電池にお
けるバインダー樹脂は、フッ素系有機重合体やスチレン
−ブタジエンゴム等のいずれも電気的な良導体ではな
く、又、イオン伝導能が特に優れているわけでもなかっ
た。イオン伝導能が不充分であると、リチウムイオンに
とって、電極領域における抵抗が大きくなってしまうと
いう問題点があった。[0005] However, the binder resin in the above-mentioned conventional lithium secondary battery is not a good electrical conductor, such as a fluorine-based organic polymer or styrene-butadiene rubber, and is not particularly excellent in ionic conductivity. Did not. If the ion conductivity is insufficient, there is a problem that the resistance in the electrode region increases for lithium ions.

【０００６】又、非水系電解液の他に、高分子電解質も
使用され得るが、これらのバインダー樹脂は、イオン伝
導層である高分子電解質との相性が考慮されているわけ
でもなかった。従って、電極領域と高分子電解質領域の
間には界面が形成されてしまうおそれがあり、不可逆な
反応が助長されやすく、電池としてのサイクル特性を損
なう可能性があった。[0006] In addition to a non-aqueous electrolyte, a polymer electrolyte can also be used, but these binder resins have not taken into consideration the compatibility with the polymer electrolyte as an ion conductive layer. Therefore, an interface may be formed between the electrode region and the polymer electrolyte region, an irreversible reaction is likely to be promoted, and the cycle characteristics of the battery may be impaired.

【０００７】更に、電極活物質から集電体への電子伝達
を充分に行うには、ＬｉＣｏＯ2 等の電極活物質や黒鉛
粉末等と集電体とがそれぞれ接触している必要がある
が、バインダー樹脂によってこれらを結合させているた
め、添加するバインダー樹脂の量が多すぎると、これら
の接触が不充分となり、従って電子伝達能も充分ではな
くなる。一方、接触を増やすためにバインダー樹脂の量
を減らすと、活物質の剥離を招来し易い。Further, in order to sufficiently transfer electrons from the electrode active material to the current collector, it is necessary that the electrode active material such as LiCoO 2 or graphite powder is in contact with the current collector. Since these are bound by the resin, if the amount of the binder resin to be added is too large, the contact between them becomes insufficient, and the electron transfer ability also becomes insufficient. On the other hand, if the amount of the binder resin is reduced to increase the contact, the active material is likely to be separated.

【０００８】一方、「ジャーナル・オブ・エレクトロケ
ミカル・ソサイエティ」(J.Electrochem.Soc.)第１４２
巻(No.12) 、４１９０頁、１９９５年には、ＬｉＭｎ2
Ｏ4とポリピロールを複合化した電池を用いた二次電池
の例が記載されているが、特に、電子伝達能は改善され
ているものの、イオン伝導を担う領域が形成されていな
いので、イオン伝導能が十分とは言えないものであっ
た。On the other hand, “Journal of Electrochemical Society” (J. Electrochem. Soc.) No. 142
Volume (No. 12), p. 4190, 1995, LiMn2
An example of a secondary battery using a battery in which O4 and polypyrrole are combined is described. In particular, although the electron transfer ability is improved, a region responsible for ionic conduction is not formed. Was not enough.

【０００９】又、「マクロモレキュールズ」(Macromole
cules)、第28巻、6250頁、1995年には、側鎖にオリゴエ
チレンオキシドを導入したポリピロールを電極活物質と
して用いた二次電池の例が記載されているが、導電性ポ
リマーを電極活物質として用いた場合はサイクル特性に
問題があり、また電解重合により上記ポリピロールを得
ているため、大面積の電極をつくるのは困難であり、従
って出力特性の不十分なものであった。[0009] Also, "Macromolecules"
cules), Vol. 28, p. 6250, 1995, describes an example of a secondary battery using polypyrrole having oligoethylene oxide introduced into a side chain as an electrode active material. When used as, there was a problem in the cycle characteristics, and since the polypyrrole was obtained by electrolytic polymerization, it was difficult to produce a large-area electrode, and thus the output characteristics were insufficient.

【００１０】[0010]

【発明が解決しようとする課題】本発明は、上記従来の
非水系のリチウム二次電池の問題点を解決するもので、
その目的とするところは、非水系二次電池、特に非水系
のリチウム二次電池に用いる、高いイオン伝導性及び電
子伝導性並びに結着能を併せ持った電極用導電助剤、こ
れを用いた二次電池の電極及び二次電池を提供すること
にある。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional non-aqueous lithium secondary battery.
The purpose is to provide a conductive auxiliary agent for an electrode having high ionic conductivity, electronic conductivity and binding ability, which is used for a non-aqueous secondary battery, particularly a non-aqueous lithium secondary battery. An object of the present invention is to provide an electrode of a secondary battery and a secondary battery.

【００１１】[0011]

【課題を解決するための手段】上記目的を達成するため
に、請求項１記載発明では、下記一般式（１）で示され
る化合物からなることを特徴とする二次電池電極用導電
助剤が提供される。According to a first aspect of the present invention, there is provided a conductive auxiliary agent for a secondary battery electrode comprising a compound represented by the following general formula (1). Provided.

【００１２】[0012]

【化３】 （式中、Ｒは１〜２０の繰り返し単位を有する一価のイ
オン伝導性有機基であり、ＸはＮＨ、Ｓ、Ｏ又はＳｅを
表す。ｎは１〜１０, ０００の整数を表す。）Embedded image (In the formula, R is a monovalent ion-conductive organic group having 1 to 20 repeating units, X represents NH, S, O or Se. N represents an integer of 1 to 10,000.)

【００１３】請求項２記載発明では、下記一般式（２）
で示される化合物からなることを特徴とする二次電池の
電極用導電助剤が提供される。According to the second aspect of the present invention, the following general formula (2)
And a conductive auxiliary agent for an electrode of a secondary battery, comprising: a compound represented by the formula:

【化４】 （式中、Ｒは、１〜２０の繰り返し単位を有する一価の
イオン伝導性有機基であり、ＸはＮＨ、Ｓ、Ｏ又はＳｅ
を表す。ｌ、ｍはともに１以上の自然数であり、ｌ＋ｍ
は２〜１０，０００の整数を表す。）Embedded image (Wherein, R is a monovalent ion-conductive organic group having 1 to 20 repeating units, and X is NH, S, O or Se
Represents l and m are natural numbers of 1 or more, and l + m
Represents an integer of 2 to 10,000. )

【００１４】請求項３記載発明では、集電体上に電極活
物質及び請求項１又は２記載の二次電池の電極用導電助
剤が含有された塗膜が形成されていることを特徴とする
二次電池の電極が提供される。請求項４記載発明では、
正極及び／又は負極が請求項３記載の二次電池の電極で
あることを特徴とする二次電池が提供される。According to a third aspect of the present invention, a coating film containing an electrode active material and a conductive assistant for an electrode of a secondary battery according to the first or second aspect is formed on a current collector. An electrode of a secondary battery is provided. In the invention described in claim 4,
A secondary battery is provided, wherein the positive electrode and / or the negative electrode are electrodes of the secondary battery according to claim 3.

【００１５】以下、本発明を更に詳細に説明する。請求
項１記載発明における一般式（１）で示される化合物に
おいて、ｎは１〜１０，０００である。ｎは１以上なら
ば、高いイオン伝導性及び電子伝導性並びに、バインダ
ーとしての結着能を発現させることができ、１０，００
０を超えると、バインダーとして固くなりすぎ、充放電
時のサイクル劣化の原因になる。好ましくは、５〜５，
０００であり、更に好ましくは、１０〜１，０００であ
る。１０未満では、バインダーとして柔らかすぎる。Hereinafter, the present invention will be described in more detail. The compound represented by the general formula (1) according to claim 1, wherein n is 1 to 10,000. When n is 1 or more, high ionic conductivity and electron conductivity, and binding ability as a binder can be exhibited, and
If it exceeds 0, it becomes too hard as a binder and causes cycle deterioration at the time of charge and discharge. Preferably, 5 to 5,
000, and more preferably 10 to 1,000. If it is less than 10, it is too soft as a binder.

【００１６】上記Ｒは、イオン伝導性有機基である。本
明細書中、イオン伝導性有機基とは、その末端を水素に
置き換えた化合物の単体でのイオン伝導率が10-7（S/c
m) 以上である有機基をいう。The above R is an ion conductive organic group. In the present specification, the ionic conductive organic group is a compound in which the terminal is replaced with hydrogen and the ionic conductivity of the compound alone is 10-7 (S / c
m) Refers to an organic group having the above.

【００１７】上記イオン伝導性有機基としては、ポリエ
チレングリコール、ポリプロピレングリコール、ポリア
ミド等の誘導体の他、例えば、ポリエチレングリコー
ル、ポリプロピレングリコール、ポリアミド等の残基、
及びこれらの誘導体の残基の他、例えば、−ＣＨ( ＣＨ
3 ) ＣＨ2 〔ＯＣＨ( ＣＨ3 ) ＣＨ2 〕x(ＯＣＨ2 ＣＨ
2 )y〔ＯＣＨ( ＣＨ3 ) ＣＨ2 〕z −（x,y,z は１以上
３０未満の整数）のごとく、イオン伝導性の良好な１種
又は２種以上のモノマーより形成された繰り返し単位を
含有した有機基等が挙げられる。Examples of the ion-conductive organic group include derivatives such as polyethylene glycol, polypropylene glycol, and polyamide, as well as residues such as polyethylene glycol, polypropylene glycol, and polyamide.
And residues of these derivatives, for example, -CH (CH
3) CH2 [OCH (CH3) CH2] x (OCH2CH
2) y [OCH (CH3) CH2] z- (x, y, z is an integer of 1 to less than 30), and a repeating unit formed of one or more monomers having good ion conductivity. And the organic group contained.

【００１８】上記で使用されるモノマーとしては、２−
ヒドロキシエチル（メタ）アクリレート、２−ヒドロキ
シプロピル（メタ）アクリレート、グリセロール（メ
タ）アクリレート、２−アクリルアミド−２−メチルプ
ロパンスルホン酸、スルホン酸ナトリウムエチル（メ
タ）アクリレート、（メタ）アクリルアミド、Ｎ，Ｎ−
ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−
ジエチルアミノエチル（メタ）アクリレート、Ｎ−イソ
プロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロ
ピルアクリルアミド、（メタ）アクリル酸、（メタ）ア
クリル酸ナトリウム、２−（メタ）アクリロイルオキシ
エチルコハク酸、２−（メタ）アクリロイルオキシエチ
ルフタル酸、２−（メタ）アクリロイルオキシエチルヘ
キサヒドロフタル酸、ω−カルボキシ−ポリカプロラク
トンモノアクリレート、エチレンオキサイド（ＥＯ）変
性リン酸（メタ）アクリレート、ポリエチレングリコー
ル（メタ）アクリレート、アクリロイルモルホリン、ｐ
−スチレンスルホン酸、ビニルスルホン酸、アリルスル
ホン酸、（メタ）アクリル酸エチルスルホン酸などが挙
げられる。The monomers used above include 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, sodium ethyl sulfonate (meth) acrylate, (meth) acrylamide, N, N −
Dimethylaminoethyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, (meth) acrylic acid, sodium (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, ω-carboxy-polycaprolactone monoacrylate, ethylene oxide (EO) -modified phosphoric acid (meth) acrylate, polyethylene glycol (meth) acrylate, acryloyl morpholine , P
-Styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, ethyl (meth) acrylatesulfonic acid and the like.

【００１９】更に、（ポリ）エチレングリコールジ（メ
タ）アクリレート（新中村化学社製；商品名ＮＫエステ
ルＡ−２００、Ａ−４００、Ａ−６００、Ａ−１００
０、４Ｇ、９Ｇ、１４Ｇ、２３Ｇ、共栄社化学社製；ラ
イトエステル４ＥＧ、９ＥＧ、１４ＥＧ、９ＥＧ−Ａ、
１４ＥＧ−Ａ等）、（ポリ）エチレングリコールモノ
（メタ）アクリレート（新中村化学社製；ＮＫエステル
ＡＭＰ−１０Ｇ、ＡＭＰ−２０Ｇ、ＡＭＰ−６０Ｇ、Ａ
ＭＰ−９０Ｇ、共栄社化学社製；ライトエステルＭＣ、
１３０ＭＡ、０４１ＭＡ等）、エトキシ化ポリプロピレ
ングリコールジメタクリレート（新中村化学社製；商品
名ＮＫエステル１２０６ＰＥ）等が挙げられる。Further, (poly) ethylene glycol di (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name: NK Ester A-200, A-400, A-600, A-100)
0, 4G, 9G, 14G, 23G, manufactured by Kyoeisha Chemical Co .; light ester 4EG, 9EG, 14EG, 9EG-A,
14EG-A), (poly) ethylene glycol mono (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester AMP-10G, AMP-20G, AMP-60G, A
MP-90G, manufactured by Kyoeisha Chemical Co .; light ester MC,
130MA, 041MA, etc.) and ethoxylated polypropylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name: NK ester 1206PE).

【００２０】上記Ｒは、例えば、―ＣＨ2 Ｏ( ＣＨ2 Ｃ
Ｈ2 Ｏ) k ＣＨ2 （繰り返し単位数k が１〜２０）等の
イオン伝導性有機基であることが好ましい。より好まし
くは、３〜１０の繰り返し単位 (k)を有するものであ
る。繰り返し単位が３未満では、リチウムイオンとの相
互作用が低下し、良好なイオン伝導が得られにくい。繰
り返し単位が１０を超えると、相対的に複素環の存在量
が減少し、電子伝達能が低下する。The above R is, for example, —CH 2 O (CH 2 C
It is preferably an ion-conductive organic group such as H2O) kCH2 (where k is 1 to 20). More preferably, it has 3 to 10 repeating units (k). If the number of repeating units is less than 3, the interaction with lithium ions decreases, and it is difficult to obtain good ionic conductivity. When the number of repeating units exceeds 10, the abundance of the heterocyclic ring relatively decreases, and the electron transfer ability decreases.

【００２１】本発明の導電助剤において、複素環の部分
は、電子伝達を担う。ポリピロール、ポリチオフェンな
どは導電性ポリマーとしてよく知られており、バインダ
ー中にこのような構造が存在することで、電極活物質と
集電体との電子伝達能を向上させることができる。Ｘは
その電気伝導度の点でＮＨが好ましく用いられる。In the conductive additive of the present invention, the part of the heterocyclic ring is responsible for electron transfer. Polypyrrole, polythiophene, and the like are well known as conductive polymers, and the presence of such a structure in the binder can improve the electron transfer ability between the electrode active material and the current collector. X is preferably NH in view of its electric conductivity.

【００２２】本発明の導電助剤において、Ｒの部分は、
イオン伝導と、バインダーとしての結着能を担う。この
部分にイオン伝導性及びバインダーとしての結着性を有
する有機基を適用することで、リチウムイオンの電極活
物質への進入、電極活物質からの排出を制限することな
く、バインダーとしての結着性を発現させることが可能
になる。In the conductive additive of the present invention, R is
Responsible for ion conduction and binding ability as a binder. By applying an organic group having ion conductivity and a binding property as a binder to this part, the binding as a binder can be performed without restricting the penetration of lithium ions into the electrode active material and the discharge from the electrode active material. Properties can be expressed.

【００２３】請求項２記載発明における一般式（２）で
示される化合物において、ｌ、ｍはともに１以上の自然
数であり、ｌ＋ｍは２〜１０，０００の整数である。こ
れは、一般式（１）で示される化合物においてｎを限定
したのと同様の考え方に基づいて限定されたものであ
る。又、ｌ又はｍが２以上の場合は、繰り返し単位がブ
ロック的に結合していても良く、ランダムに結合してい
ても良い。その他、Ｒ、Ｘ等は一般式（１）で示される
化合物と同様である。In the compound represented by the general formula (2) according to the second aspect of the present invention, l and m are each a natural number of 1 or more, and l + m is an integer of 2 to 10,000. This is limited based on the same concept as limiting n in the compound represented by the general formula (1). When l or m is 2 or more, the repeating units may be bonded in a block manner or may be randomly bonded. In addition, R, X and the like are the same as those of the compound represented by the general formula (1).

【００２４】本発明の導電助剤は、イオン伝導性能を担
う部位を有することで、正極−負極間のイオン移動媒体
である高分子電解質との相性が良いため、各層間の密着
性にも優れる。本発明の導電助剤は、二次電池電極材と
して好適に用いられる。得られた二次電池電極を用いて
所期の性能を備えた二次電池が得られる。Since the conductive additive of the present invention has a portion having ion conductivity, it has good compatibility with the polymer electrolyte which is an ion transfer medium between the positive electrode and the negative electrode, and therefore has excellent adhesion between layers. . The conductive additive of the present invention is suitably used as a secondary battery electrode material. Using the obtained secondary battery electrode, a secondary battery having the expected performance can be obtained.

【００２５】本発明の導電助剤を用いて、正極を製造す
る方法としては特に限定されず、例えば、１モルｄｍ-3
のＨＣｌＯ４の水溶液に活物質となるＬｉＭｎ2 Ｏ4 を
所望量懸濁させ、その懸濁溶液に数十分間窒素ガスをバ
ブリングしたのち、本発明の導電助剤を形成するモノマ
ーを徐々に添加する。これによって得られた固体を集電
体上にプレスする方法が挙げられる。The method for producing a positive electrode using the conductive additive of the present invention is not particularly limited. For example, 1 mol dm −3
A desired amount of LiMn2 O4 as an active material is suspended in an aqueous solution of HClO4, and a nitrogen gas is bubbled through the suspension for several tens of minutes, and then a monomer forming the conductive additive of the present invention is gradually added. A method of pressing the obtained solid on a current collector may be mentioned.

【００２６】本発明の導電助剤の添加量としては、電極
活物質１００重量部に対して、１〜２５重量部が好まし
い。上記電極活物質としては特に限定されず、例えば、
正極活物質としては、ＬｉＭｎ2 Ｏ4 やα−ＭｎＯ2 、
β−ＭｎＯ2 、更にはこれらのＭｎの一部を、Ｃｏ及び
Ｎｉ等の他元素で置換した複合酸化物等が挙げられる。The amount of the conductive additive of the present invention is preferably 1 to 25 parts by weight based on 100 parts by weight of the electrode active material. The electrode active material is not particularly limited, for example,
LiMn2 O4, α-MnO2,
.beta.-MnO2, and composite oxides in which a part of these Mn are substituted with other elements such as Co and Ni are exemplified.

【００２７】負極を製造する方法としては、例えば、負
極活物質としては、カーボン粉末や異方性ピッチを焼成
した炭素化合物、高分子繊維、芳香族化合物等が挙げら
れ、リチウム金属の場合はそのまま負極電極として用い
るが、炭素系活物質はイオン伝導性を有する高分子化合
物例えば、ポリエチレンオキシドやポリプロピレンオキ
シドまたはその誘導体をバインダーとして使用し、電極
活物質及び溶剤とともに混合してペーストを作成し、こ
れを集電体である銅箔等の金属箔に塗着、乾燥する方法
が採用される。As a method for producing the negative electrode, for example, as the negative electrode active material, carbon powder, a carbon compound obtained by calcining an anisotropic pitch, a polymer fiber, an aromatic compound and the like can be mentioned. Although used as a negative electrode, a carbon-based active material is a polymer compound having ion conductivity, for example, polyethylene oxide or polypropylene oxide or a derivative thereof is used as a binder, and mixed with an electrode active material and a solvent to form a paste. Is applied to a metal foil such as a copper foil as a current collector and dried.

【００２８】上記溶剤としては、特に限定されず、例え
ば、カルボキシメチルセルロース水溶液等が挙げられ
る。本発明においては、上記ペースト中にカーボンや金
属粉末、金属酸化物粉末等を更に混合して、電子伝導性
を高めることも可能である。The solvent is not particularly restricted but includes, for example, an aqueous solution of carboxymethylcellulose. In the present invention, electron conductivity can be enhanced by further mixing carbon, metal powder, metal oxide powder and the like in the paste.

【００２９】本発明の導電助剤は、高いイオン伝導性と
電子伝導性及びバインダーとしての結着能を有している
ので、使用に当たって、その添加量を制限することがな
く、バインダーとして用いれば、必要にして充分な量を
使用する事ができ、諸性能を更に向上させることが期待
できる。The conductive additive of the present invention has high ionic conductivity, high electron conductivity and binding ability as a binder. It can be used in a necessary and sufficient amount, and it is expected that various performances can be further improved.

【００３０】（作用）本発明の導電助剤は、２つの部分
からなり、１つは、Ｒの部分で、イオン伝導能と、バイ
ンダーとしての結着能を持ち、リチウムイオンの電極活
物質への進入、電極活物質からの排出を制限することな
く、バインダーとしての結着性を発現させることを可能
にする。もう１つは、複素環の部分であり、ポリピロー
ル、ポリチオフェンなどは導電性ポリマーとしてよく知
られており、バインダー中にこのような構造が存在する
ことで、電極活物質と集電体との電子伝達を向上させる
ことができる。これらより本発明の導電助剤を電池に適
用した場合、高容量、高エネルギー密度であり、良好な
サイクル特性を示すリチウムイオン系ポリマーバッテリ
ーを提供することが可能となるのである。(Effect) The conductive assistant of the present invention is composed of two parts, one is an R part, which has ionic conductivity and binding ability as a binder, and converts lithium ions into an electrode active material. Without restricting the ingress and discharge from the electrode active material. The other is a heterocyclic moiety, such as polypyrrole and polythiophene, which are well-known as conductive polymers. The presence of such a structure in a binder allows the electron active material and the current collector to form an electron. Communication can be improved. Thus, when the conductive additive of the present invention is applied to a battery, it is possible to provide a lithium ion polymer battery having a high capacity and a high energy density and exhibiting good cycle characteristics.

【００３１】[0031]

【実施例】以下、本発明の実施例及び比較例を説明する
が、本発明はこれら実施例のみに限定されるものではな
い。 （実施例１）この実施例では、図１に模式断面図で示す
ような試験電池Ａを作製した。EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited to only these examples. (Example 1) In this example, a test battery A as shown in the schematic sectional view of FIG. 1 was produced.

【００３２】＜モノマーの合成＞先ず本発明の導電助剤
を形成するためのモノマーを、以下の通り合成した。無
水塩化アルミニウムをジクロロエタンに懸濁させ、その
溶液にクロロアセチルクロリドを滴下し、２５℃１時間
反応させ、さらにＮ- トシルピロールのジクロロエタン
溶液を加え、更に、２５℃１時間反応させた。0.5 規定
の塩酸で反応を止め、溶液を濃縮し、その後シリカゲル
クロマトグラフィーで精製した。<Synthesis of Monomer> First, a monomer for forming the conductive additive of the present invention was synthesized as follows. Anhydrous aluminum chloride was suspended in dichloroethane, and chloroacetyl chloride was added dropwise to the solution, reacted at 25 ° C. for 1 hour, further added with a solution of N-tosylpyrrole in dichloroethane, and further reacted at 25 ° C. for 1 hour. The reaction was stopped with 0.5 N hydrochloric acid, the solution was concentrated, and then purified by silica gel chromatography.

【００３３】これにより３-(クロロアセチル)-1-トシル
ピロールが得られた。さらにこれに臭化リチウムをアル
ゴン気流下２４時間145 ℃で反応させ、冷やした後、５
規定の水酸化ナトリウム水溶液を加え、２４時間撹拌
し、その後、抽出、分離、精製を行い、３-[( ２- メト
キシエトキシ)-アセチル] ピロールを得た。更に、これ
に水素化アルミニウムリチウムと３−[(２−メトキシエ
トキシ) アセチル] ピロールをTHF 中で反応させ、これ
を分離精製し、目的のモノマーとして３−( ３, ６−ジ
オキサヘプチル) ピロールを得た。As a result, 3- (chloroacetyl) -1-tosylpyrrole was obtained. Further, this was reacted with lithium bromide at 145 ° C. for 24 hours in a stream of argon, cooled, and then cooled.
A specified aqueous sodium hydroxide solution was added, and the mixture was stirred for 24 hours. Thereafter, extraction, separation, and purification were performed to obtain 3-[(2-methoxyethoxy) -acetyl] pyrrole. Further, this is reacted with lithium aluminum hydride and 3-[(2-methoxyethoxy) acetyl] pyrrole in THF, separated and purified, and 3- (3,6-dioxaheptyl) pyrrole is obtained as a target monomer. I got

【００３４】＜正極の作製＞正極活物質としてのＬｉＭ
ｎ2 Ｏ4 の粉末７５重量部に対し、一般式（１）で示さ
れる化合物において、Ｒが―ＣＨ2 ＯＣＨ2 ＣＨ2 ＯＣ
Ｈ3 で、ＸがＮＨでｎ＝２００のものを２５重量部の割
合となる様に、前記化合物の存在下に１モルｄｍ-3ＨＣ
ｌＯ4 の水溶液に活物質となるＬｉＭｎ2 Ｏ4 を懸濁さ
せ、その懸濁溶液に数十分間窒素ガスを通気したのち、
本発明の導電助剤を形成するためのモノマーを徐々に添
加した。<Preparation of positive electrode> LiM as positive electrode active material
In the compound represented by the general formula (1), R is -CH2OCH2CH2OC with respect to 75 parts by weight of n2O4 powder.
1 mole dm -3 HC in the presence of the compound such that H3, X is NH and n = 200 is in a proportion of 25 parts by weight.
LiMn2 O4 as an active material is suspended in an aqueous solution of lO4, and nitrogen gas is passed through the suspension for several tens of minutes.
Monomers for forming the conductive additive of the present invention were gradually added.

【００３５】得られた複合体を、厚さ０．０３ｍｍのア
ルミ箔集電体の片面にプレスした片面正極板（図１にお
いてアルミ集電体１１とその片面に形成された正極活物
質層１２とからなる）１０ａと、アルミ箔集電体の両面
上にプレスした両面正極板（アルミ集電体１１とその両
面に形成された正極活物質層１２とからなる）１０ｂと
をそれぞれ１枚ずつ作成し、厚さ０．１７ｍｍ、幅４０
ｍｍ、長さ２５０ｍｍの電極板を作成した。尚、この片
面正極板１０ａ及び両面正極板１０ｂには、正極リード
線４０を取り付けた。The obtained composite was pressed on one side of an aluminum foil current collector having a thickness of 0.03 mm (FIG. 1 shows an aluminum current collector 11 and a positive electrode active material layer 12 formed on one side thereof). 10a) and a double-sided positive electrode plate (composed of an aluminum current collector 11 and a positive electrode active material layer 12 formed on both surfaces thereof) 10b pressed on both sides of an aluminum foil current collector. Created, thickness 0.17mm, width 40
An electrode plate having a length of 250 mm and a length of 250 mm was prepared. The positive electrode lead wire 40 was attached to the single-sided positive electrode plate 10a and the double-sided positive electrode plate 10b.

【００３６】＜負極の作製＞電池の負極活物質として、
ピッチを約３０００℃で焼成して作成したメソカーボン
小球体１００重量部、ポリエチレングリコールジアクリ
レート( 分子量：５０００) とポリエチレングリコール
モノアクリレート( 分子量：４００) とを６：４の重量
比率で混合したもの７重量部、リチウム塩１重量部、
１，２−ジメトキシエタン１０重量部及びγ−ブチロラ
クトン１０重量部を混合したものを、乾燥不活性ガス雰
囲気中、８：２の重量比率で混合した。<Preparation of Negative Electrode> As a negative electrode active material of a battery,
100 parts by weight of mesocarbon spheres prepared by firing the pitch at about 3000 ° C., and a mixture of polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) in a weight ratio of 6: 4. 7 parts by weight, 1 part by weight of lithium salt,
A mixture of 10 parts by weight of 1,2-dimethoxyethane and 10 parts by weight of γ-butyrolactone was mixed in a dry inert gas atmosphere at a weight ratio of 8: 2.

【００３７】これを厚さ０．０３ｍｍの銅箔上にスクリ
ーンコーティングによりキャストした。その後、乾燥不
活性ガス雰囲気中、電子線量１５Ｍｒａｄの電子線を照
射することにより上記複合負極を硬化させた。この操作
を集電体の片面に行なって片面負極板（図１において銅
集電体２１とその片面に形成された負極活物質層２２と
からなる）２０ａと、集電体の両面に行なって両面負極
板（銅集電体２１とその両面に形成された負極活物質層
２２とからなる）２０ｂとをそれぞれ１枚ずつ作成し、
厚さ０．１９ｍｍ、幅４０ｍｍ、長さ２５０ｍｍの電極
板を作成した。尚、この片面負極板２０ａ及び両面負極
板２０ｂには、負極リード線５０を取り付けた。This was cast on a 0.03 mm thick copper foil by screen coating. Thereafter, the composite negative electrode was cured by irradiating it with an electron beam having an electron dose of 15 Mrad in a dry inert gas atmosphere. This operation is performed on one side of the current collector to perform a single-sided negative electrode plate (comprising a copper current collector 21 and a negative electrode active material layer 22 formed on one side thereof in FIG. 1) 20a and both surfaces of the current collector. A double-sided negative electrode plate (comprising a copper current collector 21 and a negative electrode active material layer 22 formed on both surfaces thereof) 20b is prepared one by one,
An electrode plate having a thickness of 0.19 mm, a width of 40 mm, and a length of 250 mm was prepared. A negative electrode lead wire 50 was attached to the single-sided negative electrode plate 20a and the double-sided negative electrode plate 20b.

【００３８】＜電池の作製＞エトキシ化ポリプロピレン
グリコールジメタクリレート（新中村化学社製；商品名
ＮＫエステル１２０６ＰＥ）４０重量部、ポリエチレン
グリコールジメタクリレート（新中村化学社製；商品名
ＮＫエステル９Ｇ）２５重量部、平均分子量が約１００
０のポリエチレンオキサイド２５重量部、リチウム化合
物としてヘキサフルオロりん酸リチウム５重量部、及
び、硬化剤としてアゾビスイソブチロニトリル（ＡＩＢ
Ｎ）０．３重量部を窒素置換雰囲気下で混合し、高分子
電解質の粘性溶液を作成した。<Preparation of Battery> 40 parts by weight of ethoxylated polypropylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name: NK ester 1206PE); Parts, average molecular weight of about 100
25 parts by weight of polyethylene oxide, 5 parts by weight of lithium hexafluorophosphate as a lithium compound, and azobisisobutyronitrile (AIB) as a curing agent
N) 0.3 part by weight was mixed under a nitrogen-substituted atmosphere to prepare a viscous solution of a polymer electrolyte.

【００３９】片面正極板１０ａの正極活物質層１２上に
上記粘性溶液を塗布し、これに上記粘性溶液で満たされ
た槽に浸漬して得られた両面負極板２０ｂを重ね、次
に、上記粘性溶液で満たされた槽に浸漬して得られた両
面正極板１０ｂを重ね、最後に、片面負極板２０ａを重
ねて、窒素置換雰囲気下で８０℃で２時間かけて熱硬化
させてそれぞれの間に高分子固体電解質層３０を形成
し、正極同士及び負極同士のリード線４０及び５０を束
ねて、組電池を得た。The viscous solution is applied on the positive electrode active material layer 12 of the single-sided positive electrode plate 10a, and the double-sided negative electrode plate 20b obtained by immersing the viscous solution in a bath filled with the viscous solution is overlaid. The double-sided positive electrode plate 10b obtained by immersing in a bath filled with a viscous solution is overlapped, and finally, the single-sided negative electrode plate 20a is overlapped and thermally cured at 80 ° C. for 2 hours in a nitrogen-substituted atmosphere. A solid polymer electrolyte layer 30 was formed therebetween, and the lead wires 40 and 50 of the positive electrodes and the negative electrodes were bundled to obtain an assembled battery.

【００４０】内側にポリフッ化ビニリデンがラミネート
されているアルミ製パックからなる電池ケース６０の中
に、不活性ガスとともにこの組電池を封入し、束ねたリ
ード線の一部をを外に出し、開口部を熱融着することに
よって、図１に示すような試験電池Ａを作製した。The battery pack is sealed together with an inert gas in a battery case 60 made of an aluminum pack having polyvinylidene fluoride laminated on the inside, and a part of the bundled lead wires is taken out, and an opening is provided. A test battery A as shown in FIG. 1 was produced by heat-sealing the parts.

【００４１】＜電池の評価＞試験電池Ａの評価は、充電
電圧４．０Ｖ、充電時間１時間での低電圧充電を行い、
制限電流を６００ｍＡとした。放電は、放電電流５００
ｍＡ、放電終止電圧１．５Ｖの低電流放電を行い、２０
℃の環境下で充放電を繰り返すサイクル試験を行った。
横軸にサイクル数、縦軸に容量（ｍＡｈ）を表したグラ
フ上に結果を示し、図２とした。<Evaluation of Battery> The evaluation of the test battery A was performed by performing low voltage charging at a charging voltage of 4.0 V and a charging time of 1 hour.
The limiting current was set to 600 mA. Discharge is at a discharge current of 500
mA, a low-current discharge at a discharge end voltage of 1.5 V
A cycle test in which charge and discharge were repeated in an environment of ° C was performed.
The results are shown on a graph in which the horizontal axis represents the number of cycles and the vertical axis represents the capacity (mAh), and are shown in FIG.

【００４２】（実施例２）実施例１において、モノマー
に３−( ３, ６−ジオキサヘプチル) ピロールとピロー
ル用い、Ｒが―ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ３で、Ｘが
ＮＨでｍ＝１００、かつｌ＝１００の（２）式で示され
る導電助剤を用いた以外は、実施例１と同様にして試験
電池Ａを作製し、同様の評価を行い、結果を図２に示し
た。 （実施例３）実施例１において、モノマーに実施例１と
同様にして合成した３−( ３, ６,９−トリオキサデカ
ニル) ピロールを用い、Ｒが―ＣＨ２Ｏ( ＣＨ２ＣＨ２
Ｏ)2ＣＨ３で、ＸがＮＨでｎ＝２００の（１）式で示さ
れる導電助剤を用いた以外は、実施例１と同様にして試
験電池Ａを作製し、同様の評価を行い、結果を図２に示
した。(Example 2) In Example 1, 3- (3,6-dioxaheptyl) pyrrole and pyrrole were used as monomers, R was -CH2OCH2CH2OCH3, X was NH, m = 100 and 1 = 100. A test battery A was prepared in the same manner as in Example 1 except that the conductive aid represented by the formula (2) was used, and the same evaluation was performed. The results are shown in FIG. (Example 3) In Example 1, 3- (3,6,9-trioxadecanyl) pyrrole synthesized in the same manner as in Example 1 was used as the monomer, and R was -CH2O (CH2CH2).
O) 2CH3, a test battery A was prepared and evaluated in the same manner as in Example 1 except that the conductive aid represented by the formula (1) was used, wherein X was NH and n = 200. Is shown in FIG.

【００４３】（実施例４）実施例１においてモノマーに
３−( ３, ６, ９−トリオキサデカニル) ピロールとピ
ロール用い、Ｒが―ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ３で、
ＸがＮＨでｍ＝１４０、かつｌ＝６０の（２）式で示さ
れる導電助剤を用いた以外は、実施例１と同様にして試
験電池Ａを作製し、同様の評価を行い、結果を図２に示
した。 （実施例５）実施例１においてモノマーに３−( ３,
６, ９−トリオキサデカニル) ピロールとピロール用
い、Ｒが―ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ３で、ＸがＮＨ
でｍ＝１００、かつｌ＝１００の（２）式で示される導
電助剤を用いた以外は、実施例１と同様にして試験電池
Ａを作製し、同様の評価を行い、結果を図２に示した。(Example 4) In Example 1, 3- (3,6,9-trioxadecanyl) pyrrole and pyrrole were used as monomers, R was -CH2OCH2CH2OCH3,
A test battery A was prepared and evaluated in the same manner as in Example 1, except that the conductive auxiliary represented by the formula (2) where X was NH and m = 140 and 1 = 60 was used. Is shown in FIG. (Example 5) In Example 1, 3- (3,
6,9-trioxadecanyl) pyrrole and pyrrole, where R is —CH 2 OCH 2 CH 2 OCH 3 and X is NH
A test battery A was prepared in the same manner as in Example 1 except that the conductive aid represented by the formula (2) where m = 100 and 1 = 100 was used, and the same evaluation was performed. It was shown to.

【００４４】（比較例１）実施例１において、モノマー
にピロールを用い、得られた固体がＬｉＭｎ2 Ｏ４７５
重量部ポリピロール１５重量部となるようにし、これに
にバインダーとしてテフロン（Ｃ−５５：旭硝子社製）
１０重量部を加え、プレスして電極を作製した以外は、
実施例１及び実施例３と同様にして試験電池を作製し、
同様の評価を行い、結果を図２に示した。 （比較例２）正極活物質としてＬｉＭｎ2 Ｏ４を７５重
量部使用し、導電剤としてアセチレンブラック２０重量
部を使用し、バインダーとしてポリフッ化ビニリデン樹
脂（呉羽化学社製）を５重量部使用し、Ｎ- メチルピロ
リドンでこれらの材料を分散し、集電体に塗布乾燥した
以外は、実施例１と同様にして試験電池を作製し、同様
の評価を行い、結果を図２に示した。Comparative Example 1 In Example 1, pyrrole was used as a monomer, and the resulting solid was LiMn 2 O475.
Parts by weight of polypyrrole and 15 parts by weight of Teflon as a binder (C-55: manufactured by Asahi Glass Co., Ltd.)
Except for adding 10 parts by weight and pressing to produce an electrode,
A test battery was prepared in the same manner as in Example 1 and Example 3,
The same evaluation was performed, and the results are shown in FIG. Comparative Example 2 75 parts by weight of LiMn2 O4 was used as a positive electrode active material, 20 parts by weight of acetylene black was used as a conductive agent, and 5 parts by weight of a polyvinylidene fluoride resin (manufactured by Kureha Chemical Co., Ltd.) was used as a binder. -A test battery was prepared and evaluated in the same manner as in Example 1 except that these materials were dispersed in methylpyrrolidone and applied and dried on the current collector, and the same evaluation was performed. The results are shown in FIG.

【００４５】図２から、実施例１〜５で得られた試験電
池は比較例１及び２で得られた試験電池に比して、容量
及びサイクル特性にすぐれていることが明らかである。FIG. 2 clearly shows that the test batteries obtained in Examples 1 to 5 have better capacity and cycle characteristics than the test batteries obtained in Comparative Examples 1 and 2.

【００４６】[0046]

【発明の効果】本発明の二次電池の電極用導電助剤は、
上述の構成となされ、一般式（１）又は（２）で示され
る化合物からなるので、非水系二次電池、特に非水系の
リチウム二次電池に用いられて、良好な電子伝達機能及
び良好なイオン伝導機能、並びに、バインダーとしての
結着能を併わせ持った高分子固体電解質性導電助剤を提
供することができる。また、これと電極活物質とを用い
ることによって、集電体上に電極活物質及び本発明導電
助剤が含有された塗膜が形成された二次電池の電極が提
供されるので、電極活物質から集電体への電子伝達、リ
チウムイオンの電極活物質への進入、及び、電極活物質
からの排出の効率を向上でき、バインダーとしての結着
性及び高分子電解質との界面特性が良好になる。更にか
かる電極（正極及び／又は負極）を電池に適用した場
合、高容量、高エネルギー密度であり、良好なサイクル
特性を示すリチウムイオン系ポリマーバッテリーを提供
することが可能となる。The conductive auxiliary agent for an electrode of a secondary battery according to the present invention comprises:
Since it is configured as described above and is made of the compound represented by the general formula (1) or (2), it is used for a non-aqueous secondary battery, particularly a non-aqueous lithium secondary battery, and has a good electron transfer function and a good It is possible to provide a solid polymer electrolyte conductive auxiliary agent having both an ion conduction function and a binding ability as a binder. Further, by using this and the electrode active material, an electrode of a secondary battery in which a coating film containing the electrode active material and the conductive additive of the present invention is formed on a current collector is provided. The efficiency of electron transfer from the substance to the current collector, penetration of lithium ions into the electrode active material, and discharge from the electrode active material can be improved, and the binding properties as a binder and the interface properties with the polymer electrolyte are good. become. Furthermore, when such an electrode (a positive electrode and / or a negative electrode) is applied to a battery, it is possible to provide a lithium ion polymer battery having a high capacity and a high energy density and exhibiting good cycle characteristics.

【図面の簡単な説明】[Brief description of the drawings]

【図１】実施例及び比較例で作製した試験電池の模式断
面図。FIG. 1 is a schematic cross-sectional view of test batteries manufactured in Examples and Comparative Examples.

【図２】実施例及び比較例でのサイクル試験の結果を示
すグラフ。FIG. 2 is a graph showing the results of cycle tests in Examples and Comparative Examples.

【符号の説明】[Explanation of symbols]

１０ａ 片面正極板 １０ｂ 両面正極板 １１ アルミ箔集電体 １２ 正極活物質層 ２０ａ 片面負極板 ２０ｂ 両面負極板 ２１ 銅箔集電体 ２２ 負極活物質層 ３０ 高分子固体電解質層 ４０ 正極リード線 ５０ 負極リード線 ６０ 電池ケース Reference Signs List 10a single-sided positive electrode plate 10b double-sided positive electrode plate 11 aluminum foil current collector 12 positive electrode active material layer 20a single-sided negative electrode plate 20b double-sided negative electrode plate 21 copper foil current collector 22 negative electrode active material layer 30 polymer solid electrolyte layer 40 positive electrode lead wire 50 negative electrode Lead wire 60 Battery case

───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H003 AA02 AA04 AA06 AA08 BB01 BB14 BC05 BD00 BD03 5H029 AJ03 AJ05 AJ11 AJ14 AK02 AK03 AL06 AL08 AL12 AM01 AM16 BJ04 BJ12 DJ08 DJ11 EJ11 HJ02 HJ12  ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H003 AA02 AA04 AA06 AA08 BB01 BB14 BC05 BD00 BD03 5H029 AJ03 AJ05 AJ11 AJ14 AK02 AK03 AL06 AL08 AL12 AM01 AM16 BJ04 BJ12 DJ08 DJ11 EJ11 HJ02 HJ12

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 下記一般式（１）で示される化合物から
なることを特徴とする二次電池の電極用導電助剤。 【化１】 （式中、Ｒは１〜２０の繰り返し単位を有する一価のイ
オン伝導性有機基であり、ＸはＮＨ、Ｓ、Ｏ又はＳｅを
表す。ｎは１〜１０, ０００の整数を表す。）1. A conductive assistant for an electrode of a secondary battery, comprising a compound represented by the following general formula (1). Embedded image (In the formula, R is a monovalent ion-conductive organic group having 1 to 20 repeating units, X represents NH, S, O or Se. N represents an integer of 1 to 10,000.) 【請求項２】 下記一般式（２）で示される化合物から
なることを特徴とする二次電池の電極用導電助剤。 【化２】 （式中、Ｒは、１〜２０の繰り返し単位を有する一価の
イオン伝導性有機基であり、ＸはＮＨ、Ｓ、Ｏ又はＳｅ
を表す。ｌ、ｍはともに１以上の自然数であり、ｌ＋ｍ
は２〜１０，０００の整数を表す。）2. A conductive assistant for an electrode of a secondary battery, comprising a compound represented by the following general formula (2). Embedded image (Wherein, R is a monovalent ion-conductive organic group having 1 to 20 repeating units, and X is NH, S, O or Se
Represents l and m are natural numbers of 1 or more, and l + m
Represents an integer of 2 to 10,000. ) 【請求項３】 集電体上に電極活物質及び請求項１又は
２記載の二次電池の電極用導電助剤が含有された塗膜が
形成されていることを特徴とする二次電池の電極。3. A secondary battery according to claim 1, wherein a coating containing the electrode active material and the conductive assistant for an electrode of the secondary battery according to claim 1 or 2 is formed on the current collector. electrode. 【請求項４】 正極及び／又は負極が請求項３記載の二
次電池の電極であることを特徴とする二次電池。4. A secondary battery, wherein the positive electrode and / or the negative electrode are electrodes of the secondary battery according to claim 3.
JP10307048A 1998-10-28 1998-10-28 Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery Pending JP2000133269A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10307048A JP2000133269A (en) 1998-10-28 1998-10-28 Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10307048A JP2000133269A (en) 1998-10-28 1998-10-28 Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery

Publications (1)

Publication Number Publication Date
JP2000133269A true JP2000133269A (en) 2000-05-12

Family

ID=17964431

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10307048A Pending JP2000133269A (en) 1998-10-28 1998-10-28 Electrode conductive auxiliary for secondary battery, electrode for secondary battery and secondary battery

Country Status (1)

Country Link
JP (1) JP2000133269A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010116475A (en) * 2008-11-12 2010-05-27 Adeka Corp New polymer and nonaqueous electrolyte secondary battery using the same
US7883798B2 (en) 2001-07-19 2011-02-08 Samsung Sdi Co., Ltd. Active material for battery and method of preparing the same
JP2013227578A (en) * 2013-05-09 2013-11-07 Adeka Corp Novel polymer and nonaqueous electrolyte secondary battery using the same
WO2023054367A1 (en) * 2021-09-30 2023-04-06 日産化学株式会社 Composition for forming electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7883798B2 (en) 2001-07-19 2011-02-08 Samsung Sdi Co., Ltd. Active material for battery and method of preparing the same
JP2010116475A (en) * 2008-11-12 2010-05-27 Adeka Corp New polymer and nonaqueous electrolyte secondary battery using the same
JP2013227578A (en) * 2013-05-09 2013-11-07 Adeka Corp Novel polymer and nonaqueous electrolyte secondary battery using the same
WO2023054367A1 (en) * 2021-09-30 2023-04-06 日産化学株式会社 Composition for forming electrode

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