JPH06124708A - Conductive composition containing polyvinylidene fluoride and battery using the composition - Google Patents
Conductive composition containing polyvinylidene fluoride and battery using the compositionInfo
- Publication number
- JPH06124708A JPH06124708A JP4296396A JP29639692A JPH06124708A JP H06124708 A JPH06124708 A JP H06124708A JP 4296396 A JP4296396 A JP 4296396A JP 29639692 A JP29639692 A JP 29639692A JP H06124708 A JPH06124708 A JP H06124708A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- polyvinylidene fluoride
- polyaniline
- battery
- conductive
- 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
Links
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は可溶性導電性高分子及び
ポリフッ化ビニリデンからなる導電性組成物、及びそれ
を電池用電極の結着剤に用いることを特徴とする電池に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive composition composed of a soluble conductive polymer and polyvinylidene fluoride, and a battery using the same as a binder for a battery electrode.
【０００２】[0002]
【従来技術】ポリアニリンは導電性、酸化還元特性を有
することから、導電材料、電磁波シールド、センサー、
電池、コンデンサー等への応用が検討されている。しか
しながら、ポリアニリンは膜としての強度に劣るため種
々の検討が行われている。例えば、第２８回電池討論会
予稿集、Ｐ１２５（１９８７）ではポリアニリンをＮ−
メチルピロリドンに溶解し、キャストによりポリアニリ
ンフィルムを得る方法が提案されている。しかしながら
ポリアニリンフィルムの強度が十分でなく、基板との密
着性も十分でない。また、ＷＯ９０／１３６０１公報で
はポリアニリンとポリアミドをギ酸に溶解させキャスト
により高強度ポリアニリン／ポリアミドの組成物を得る
方法が提案されている。しかしながら、溶媒にギ酸を用
いなければならないため基板、機器の腐食の問題があ
る。また、粉末活物質を用いた電池においてはポリフッ
化ビニリデンの安定性、耐溶媒性、結着性に優れること
を利用し、電極の結着剤として用いられている。しかし
ながら、電極反応を行なうためには電極の導電性を高く
する必要があるが、ポリフッ化ビニリデンは絶縁性であ
るため、電極作製には多量の導電剤を使用する必要があ
り、導電性を有する結着剤が求められていた。2. Description of the Related Art Since polyaniline has conductivity and redox properties, it is used as a conductive material, an electromagnetic wave shield, a sensor,
Applications to batteries, capacitors, etc. are under consideration. However, since polyaniline is inferior in strength as a film, various studies have been conducted. For example, in P125 (1987) of the 28th Battery Symposium Proceedings, polyaniline was used as N-
A method of obtaining a polyaniline film by dissolving it in methylpyrrolidone and casting it has been proposed. However, the strength of the polyaniline film is not sufficient, and the adhesion with the substrate is not sufficient. Further, WO 90/13601 proposes a method of obtaining a high-strength polyaniline / polyamide composition by dissolving polyaniline and polyamide in formic acid and casting. However, since formic acid must be used as a solvent, there is a problem of corrosion of substrates and equipment. Further, in a battery using a powdered active material, it has been used as a binder for electrodes by utilizing the excellent stability, solvent resistance and binding property of polyvinylidene fluoride. However, in order to carry out the electrode reaction, it is necessary to increase the conductivity of the electrode, but since polyvinylidene fluoride is insulative, it is necessary to use a large amount of a conductive agent for electrode preparation, and it has conductivity. A binder was sought.
【０００３】[0003]
【本発明が解決しようとする課題】本発明の１つの目的
は、ポリアニリンの特色を生かしつつ、それ自体の強度
と接着性を改良した組成物を提供する点にある。本発明
の他の目的は、ポリフッ化ビニリデンの特色を生かした
組成物を提供する点にある。また、本発明のもう１つの
目的は、該組成物を電極形成用等の結着剤として使用す
る点にある。SUMMARY OF THE INVENTION One object of the present invention is to provide a composition which has the characteristics of polyaniline while improving its strength and adhesiveness. Another object of the present invention is to provide a composition that takes advantage of the characteristics of polyvinylidene fluoride. Another object of the present invention is to use the composition as a binder for forming electrodes.
【０００４】[0004]
【課題を解決するための手段】本発明は、可溶性導電性
高分子とポリフッ化ビニリデンからなる導電性組成物に
関する。The present invention relates to a conductive composition comprising a soluble conductive polymer and polyvinylidene fluoride.
【０００５】前記可溶性導電性高分子とは、ポリフッ化
ビニリデンの溶媒に可溶性の導電性高分子を意味する。
具体的にはポリフッ化ビニリデンはジメチルホルムアミ
ド、Ｎ−メチルピロリドン、テトラヒドロフラン等の溶
媒に可溶な導電性高分子であれば差し支えない。この種
の導電性高分子は、例えばつぎのような単量体を重合さ
せることにより得ることができる。すなわち、 （１）アニリン類 特開昭６１−１９７６３３、特開平１−３０１７１４、
特開平２−１６６１６５、特開平２−２１１２３０、特
開平２−２２０３７３、特表平３−５０５８９２等参
照。 （２）アニリノアニリン類 例えば、式The soluble conductive polymer means a conductive polymer soluble in a solvent of polyvinylidene fluoride.
Specifically, polyvinylidene fluoride may be a conductive polymer soluble in a solvent such as dimethylformamide, N-methylpyrrolidone and tetrahydrofuran. This type of conductive polymer can be obtained, for example, by polymerizing the following monomers. That is, (1) anilines, JP-A-61-197633, JP-A-1-301714,
See JP-A-2-166165, JP-A-2-211230, JP-A-2-220373, and JP-A-3-505892. (2) Anilinoanilines For example, the formula
【化１】 （式中、Ｒ1やＲ2は水素、アルキルまたはアルコキシで
あることができる） （３）ピロール類 例えば、式[Chemical 1] (In the formula, R 1 and R 2 can be hydrogen, alkyl or alkoxy.) (3) Pyrroles
【化２】 （式中、Ｒ3、Ｒ4、Ｒ5は水素、アルキルおよびアルコ
キシよりなる群から選ばれた基であるが、Ｒ3、Ｒ4、Ｒ
5のうちの少なくとも１つはアルキルまたはアルコキシ
である） （４）チオフェン類 例えば、式[Chemical 2] (In the formula, R 3 , R 4 and R 5 are groups selected from the group consisting of hydrogen, alkyl and alkoxy, and R 3 , R 4 and R 5
At least one of 5 is alkyl or alkoxy) (4) Thiophenes
【化３】 （式中、Ｒ6とＲ7は水素、アルキルおよびアルコキシよ
りなる群から選ばれた基であるが、Ｒ6とＲ7のうち少な
くとも１つはアルキルまたはアルコキシである）などを
挙げることができる。前記〔化１〕のモノマーからは、
式[Chemical 3] (In the formula, R 6 and R 7 are groups selected from the group consisting of hydrogen, alkyl and alkoxy, but at least one of R 6 and R 7 is alkyl or alkoxy) and the like. . From the monomer of [Chemical Formula 1],
formula
【化４】 のポリマーが、前記〔化２〕のモノマーからは、式[Chemical 4] From the monomer of the above [Chemical formula 2]
【化５】 のポリマーが、前記〔化３〕のモノマーからは、式[Chemical 5] From the monomer of the above [Chemical formula 3]
【化６】 のポリマーが、それぞれ得られる。導電性や強度等を考
慮するとポリアニリン類が好適である。[Chemical 6] Polymers are obtained respectively. Polyanilines are preferable in consideration of conductivity and strength.
【０００６】本発明の導電性組成物における可溶性導電
性高分子はドープ状態、脱ドープ状態、いずれの状態の
ものも用いることができる。脱ドープ状態の可溶性導電
性高分子は溶媒への溶解性が大きいが導電性を付与する
ためにポリフッ化ビニリデンと複合後、ドーピングを行
う必要がある。ドーピングに用いるドーパントとして
は、特表平３−５０５８９２、特開平１−３０１７１
４、特開平２−１６６１６５、特開平２−２１１２３
０、特開平２−２２０３７３に記載されているようなド
ーパントが使用できる。具体例を挙げれば、塩酸、硫
酸、過塩素酸、硝酸、ホウフッ酸、塩素、臭素、ヨウ
素、塩化水素等のハロゲンアニオン、ヘキサフルオロリ
ン、ヘキサフルオロヒ素、テトラフルオロホウ素等のハ
ロゲン化物アニオン、アルキルベンゼンスルホン酸、ベ
ンゼンスルホン酸、ニトロベンゼンスルホン酸、β−ナ
フタレンスルホン酸等のスルホン酸アニオン、過塩素
酸、過塩素酸カリウム等の過塩素酸アニオン、硫酸等の
硫酸アニオン、クロマニル、ブロマニル、ジクロロベン
ゾキノン、ベンゾキノン、アントラキノン、トルキノ
ン、テトラメチル−ｐ−ベンゾキノン、テトラフルオロ
テトラシアノキノジメタン、テトラシアノキノジメタ
ン、テトラシアノエチレン、２，３−ジクロロ−５，６
−ジシアノ−ｐ−ベンゾキノン等の有機アクセプターが
挙げられ、これらは単独または混合して用いられ、ドー
ピング処理も前記公報記載の処理方法がすべて使用でき
る。１つの具体的方法としては前記ドーパントを含む化
合物と脱ドープ状態の可溶性導電性高分子を接触するこ
とにより得られる。この中でも特に導電性、腐食性、強
度を考慮すると、有機アクセプターが最も好ましい。前
記ドーピング方法により作製したドープ状態の可溶性導
電性高分子を用いる場合は一般に溶媒への溶解性が脱ド
ープ状態のものに比べ劣るが、有機アクセプターをドー
プさせた可溶性導電性高分子は溶媒への溶解性が高く、
組成物の導電性、強度が高く好ましい。The soluble conductive polymer in the conductive composition of the present invention may be in a doped or undoped state. The soluble conductive polymer in the undoped state has a high solubility in a solvent, but in order to impart conductivity, it is necessary to perform doping after compounding with polyvinylidene fluoride. As a dopant used for doping, Japanese Patent Laid-Open No. 3-505892 and Japanese Patent Laid-Open No. 30171/1991.
4, JP-A-2-166165, JP-A-2-21123
No. 0, a dopant as described in JP-A-2-220373 can be used. Specific examples include halogen anions such as hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, borofluoric acid, chlorine, bromine, iodine and hydrogen chloride, halide anions such as hexafluoroline, hexafluoroarsenic and tetrafluoroboron, and alkylbenzene. Sulfonic acid, benzenesulfonic acid, nitrobenzenesulfonic acid, sulfonate anion such as β-naphthalenesulfonic acid, perchloric acid, perchlorate anion such as potassium perchlorate, sulfate anion such as sulfuric acid, chromanyl, bromanil, dichlorobenzoquinone, Benzoquinone, anthraquinone, toluquinone, tetramethyl-p-benzoquinone, tetrafluorotetracyanoquinodimethane, tetracyanoquinodimethane, tetracyanoethylene, 2,3-dichloro-5,6
Examples thereof include organic acceptors such as -dicyano-p-benzoquinone, which may be used alone or in combination, and the doping treatment may be performed by any of the treatment methods described in the above publications. As one specific method, it can be obtained by contacting a compound containing the dopant with a soluble conductive polymer in a dedoped state. Among these, organic acceptors are most preferable in consideration of conductivity, corrosiveness and strength. When using a soluble conductive polymer in a doped state prepared by the above-mentioned doping method, the solubility in a solvent is generally inferior to that in a dedoped state, but a soluble conductive polymer doped with an organic acceptor does not dissolve in a solvent. High solubility,
The composition is preferable because of its high conductivity and strength.
【０００７】本発明における組成物中の可溶性導電性高
分子の量としては１〜９９重量％、好ましくは５〜９５
重量％、とくに好ましくは２０〜９０重量％である。The amount of the soluble conductive polymer in the composition of the present invention is 1 to 99% by weight, preferably 5 to 95%.
%, Particularly preferably 20 to 90% by weight.
【０００８】次に本発明の組成物の製造方法について述
べる。本発明の組成物は可溶性導電性高分子及びポリフ
ッ化ビニリデンを溶媒に溶解後、溶媒を除去することに
より均質な可溶性導電性高分子／ポリフッ化ビニリデン
組成物を得ることができる。可溶性導電性高分子及びポ
リフッ化ビニリデンの溶媒としてはＮ−メチルピロリド
ン、テトラヒドロフラン、ジメチルホルムアミド等を例
示することができる。溶媒の除去方法としては、加熱あ
るいは減圧による蒸発、可溶性導電性高分子及びポリフ
ッ化ビニリデン双方をほとんど溶解しない溶媒への接触
等により除去することができ、求める組成物の形状、強
度等により適宜製造法が選択される。本発明の組成物は
フィルム状、粉末状、繊維状に加工することができる。
また本発明の組成物は結着性を有するため加圧成型、加
熱成型等を行うことにより種々の形状に加工することが
でき、各種粉体活物質（例えば、無機酸化物粉体、無機
カルコゲン化合物粉体、導電性高分子粉体等）の結着剤
として用いることができる。Next, a method for producing the composition of the present invention will be described. The composition of the present invention can obtain a homogeneous soluble conductive polymer / polyvinylidene fluoride composition by dissolving the soluble conductive polymer and polyvinylidene fluoride in a solvent and then removing the solvent. Examples of the solvent for the soluble conductive polymer and polyvinylidene fluoride include N-methylpyrrolidone, tetrahydrofuran, dimethylformamide and the like. As a method for removing the solvent, the solvent can be removed by evaporation by heating or reduced pressure, contact with a solvent that hardly dissolves both the soluble conductive polymer and polyvinylidene fluoride, and the shape and strength of the desired composition. The law is selected. The composition of the present invention can be processed into a film, powder or fiber.
Further, since the composition of the present invention has a binding property, it can be processed into various shapes by performing pressure molding, heat molding, etc., and various powder active materials (eg, inorganic oxide powder, inorganic chalcogen). Compound powder, conductive polymer powder, etc.).
【０００９】さらに、前記可溶性導電性高分子、ポリフ
ッ化ビニリデン、溶媒からなる溶液には他の任意の粉体
を分散することができ、その粉体を分散させた溶液から
溶媒を除去することにより粉体を含有した可溶性導電性
高分子／ポリフッ化ビニリデン組成物を得ることができ
る。本発明の組成物に含有可能な粉体の量としては０〜
９５％、好ましくは５〜９０％である。本発明の組成物
に含有させる粉体としては各種導電性材料、光機能性材
料、電池材料等の材料を用いることができる。Further, any other powder can be dispersed in the solution containing the soluble conductive polymer, polyvinylidene fluoride and the solvent, and the solvent is removed from the solution in which the powder is dispersed. A soluble conductive polymer / polyvinylidene fluoride composition containing powder can be obtained. The amount of powder that can be contained in the composition of the present invention is 0 to
95%, preferably 5 to 90%. As the powder to be contained in the composition of the present invention, various conductive materials, optical functional materials, battery materials and the like can be used.
【００１０】次に本発明の組成物の最も効果があるケー
スとしては電池の電極用結着剤に用いた場合である。以
下これについて述べる。電極の活物質としての正極活物
質としては本発明の可溶性導電性高分子／ポリフッ化ビ
ニリデン組成物も活物質として機能するが、Ｍｎ、Ｃ
ｏ、Ｎｉ、Ｖ、Ｍｏ、Ｗ等の遷移金属の酸化物、カルコ
ゲン化合物、アルカリ金属との複合酸化物、あるいはポ
リアセチレン、ポリピロール、ポリチオフェン、ポリカ
ルバゾール、ポリアズレン等の導電性高分子、炭素体等
を例示することができる。負極活物質としてはＬｉとＡ
ｌ、Ｍｎ、Ｐｂ等の合金、炭素体等を例示することがで
きる。The most effective case of the composition of the present invention is when it is used as a binder for battery electrodes. This will be described below. As the positive electrode active material as the electrode active material, the soluble conductive polymer / polyvinylidene fluoride composition of the present invention also functions as the active material, but Mn, C
oxides of transition metals such as o, Ni, V, Mo and W, chalcogen compounds, composite oxides with alkali metals, conductive polymers such as polyacetylene, polypyrrole, polythiophene, polycarbazole and polyazulene, carbon bodies, etc. It can be illustrated. Li and A as the negative electrode active material
Examples thereof include alloys such as 1, Mn, and Pb, carbon bodies, and the like.
【００１１】次に前記電極を用いた場合の電池について
述べる。この電池は基本的には、正極、負極、電解質か
ら構成される。本発明の電池は正極として本発明組成物
を結着剤として成形した電極が用いられる。負極として
は前記電極のほか、Ｌｉ、Ｎａ、Ｋ等のアルカリ金属、
ＬｉとＡｌ、Ｍｎ、Ｐｂ等の合金、炭素体等を使用する
ことができる。Next, a battery using the above electrode will be described. This battery is basically composed of a positive electrode, a negative electrode and an electrolyte. In the battery of the present invention, an electrode formed by using the composition of the present invention as a binder is used as the positive electrode. As the negative electrode, in addition to the above electrodes, alkali metals such as Li, Na and K
An alloy of Li and Al, Mn, Pb, or the like, a carbon body, or the like can be used.
【００１２】前記電解質としては、以下に示す陰イオン
または陽イオンが用いられる。陰イオンとしては、例え
ばＰＦ6 -、ＳｂＦ6 -、Ａｓ6 -等のＶａ族の元素のハロゲ
ン化物アニオン、ＢＦ4 -、ＢＲ4 - （Ｒはフェニル基、
アルキル基）等のIIIａ族元素のアニオン、Ｃｌ-、Ｂｒ
-、Ｉ- 等のハロゲンアニオン、過塩素酸アニオン、ト
リフルオロメタンスルホン酸アニオン等が挙げられる。
陽イオンとしては例えばＬｉ+、Ｎａ+、Ｋ+ 等のアルカ
リ金属カチオン、（Ｒ4Ｎ）+（Ｒは炭素数１〜２０の炭
化水素基）等が挙げられる。前記電解質を与える化合物
としてはたとえば、ＬｉＰＦ6、ＬｉＳｂＦ6、ＬｉＡｓ
6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、Ｌｉ
Ｉ、ＫＰＦ6、ＫＣｌＯ4、ＮａＰＦ6、〔（ｎ−Ｂｕ）4
Ｎ〕ＢＦ4、〔（ｎ−Ｂｕ）4Ｎ〕ＣｌＯ4、ＬｉＡｌＣ
ｌ4等を例示することができるが特にこれらに限定され
るものではない。The following anions or cations are used as the electrolyte. Examples of the anion include halide anions of Va group elements such as PF 6 − , SbF 6 − , As 6 − , BF 4 − , BR 4 − (R is a phenyl group,
Anions of group IIIa elements such as alkyl groups), Cl − , Br
- , I-, and other halogen anions, perchlorate anions, trifluoromethanesulfonate anions, and the like.
For example Li + as a cation, Na +, K +, etc. of an alkali metal cation, (R 4 N) + ( R is a hydrocarbon group having 1 to 20 carbon atoms) and the like. Examples of the compound that provides the electrolyte include LiPF 6 , LiSbF 6 , and LiAs.
6 , LiBF 4 , LiClO 4 , LiCF 3 SO 3 , Li
I, KPF 6 , KClO 4 , NaPF 6 , [(n-Bu) 4
N] BF 4 , [(n-Bu) 4 N] ClO 4 , LiAlC
Examples thereof include l 4 and the like, but the invention is not limited thereto.
【００１３】電解質溶液を構成する溶媒は特に限定する
ものではないが、比較的、極性の大きい溶媒が好適に用
いられる。具体的には、プロピレンカーボネート、エチ
レンカーボネート、ベンゾニトリル、アセトニトリル、
テトラヒドロフラン、２−メチルテトラヒドロフラン、
γ−ブチルラクトン、ジオキソラン、トリエチルホスフ
ァイト、ジメチルホルムアミド、ジメチルアセトアミ
ド、ジメチルスルホキシド、ジオキサン、ジメトキシエ
タン、ポリエチレングリコール、スルホラン、ジクロロ
エタン、クロルベンゼン、ニトロベンゼン等の有機溶媒
の１種又は２種以上の混合液が挙げられる。The solvent constituting the electrolyte solution is not particularly limited, but a solvent having a relatively large polarity is preferably used. Specifically, propylene carbonate, ethylene carbonate, benzonitrile, acetonitrile,
Tetrahydrofuran, 2-methyltetrahydrofuran,
One or a mixture of two or more organic solvents such as γ-butyl lactone, dioxolane, triethyl phosphite, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, dimethoxyethane, polyethylene glycol, sulfolane, dichloroethane, chlorobenzene and nitrobenzene. Is mentioned.
【００１４】セパレータとしては、電解質溶液のイオン
移動に対して低抵抗であり、かつ、溶液保持性に優れた
ものが用いられ、例えば、ガラス繊維フィルタ、ポリエ
ステル、テフロン、ポリフロン、ポリプロピレン等の高
分子ボアフィルタ不織布、あるいは、ガラス繊維とこれ
らの高分子からなる不織布等が挙げられる。また、これ
ら電解液、セパレータのかわりに用いられるものとし
て、固体電解質が挙げられる。例えば、無機系では、Ａ
ｇＣｌ、ＡｇＢｒ、ＡｇＩ、ＬｉＩ等の金属ハロゲン化
物、ＲｂＡｇ4Ｉ5、ＲｂＡｇ4Ｉ4ＣＮ等が挙げられる。
また、有機系では、ポリエチレンオキサイド、ポリプロ
ピレンオキサイド、ポリフッ化ビニリデン、ポリアクリ
ルアミド等をポリマーマトリクスとし、前記の電解質塩
をポリマーマトリクス中に溶解した複合体、あるいはこ
れらのゲル架橋体、低分子量ポリエチレンオキサイド、
クラウンエーテル等のイオン解離基をポリマー主鎖にグ
ラフト化した高分子固体電解質、あるいは高分子量重合
体に前記電解液を含有させたゲル状高分子固体電解質が
挙げられる。その１つの具体例としては、本出願人の特
願昭６０−１７２０３６記載のセパレータ等がある。本
発明の電池の形態は特に限定するものではないが、コイ
ン型、シート型、円筒型、ガム型等の各種電池に実装す
ることができる。As the separator, one having a low resistance to the movement of ions of the electrolyte solution and an excellent solution holding property is used. For example, a polymer such as a glass fiber filter, polyester, Teflon, polyflon, polypropylene or the like is used. Examples thereof include a bore filter non-woven fabric or a non-woven fabric made of glass fiber and these polymers. A solid electrolyte is used as a substitute for the electrolytic solution and the separator. For example, in an inorganic system, A
Examples thereof include metal halides such as gCl, AgBr, AgI and LiI, RbAg 4 I 5 and RbAg 4 I 4 CN.
Further, in the organic system, polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, polyacrylamide and the like as a polymer matrix, a complex in which the electrolyte salt is dissolved in the polymer matrix, or a gel cross-linked product thereof, a low molecular weight polyethylene oxide,
Examples thereof include a polymer solid electrolyte in which an ionic dissociation group such as crown ether is grafted to the polymer main chain, or a gel polymer solid electrolyte in which the electrolyte solution is contained in a high molecular weight polymer. One specific example thereof is a separator described in Japanese Patent Application No. 60-172036 of the present applicant. The form of the battery of the present invention is not particularly limited, but the battery can be mounted on various batteries such as a coin type, a sheet type, a cylinder type and a gum type.
【００１５】[0015]
ポリアニリンの製造 過硫酸アンモニウムと塩酸からＡ．Ｇ．ＭａｃＤｉａｒ
ｍｉｄ ｅｔ ａｌ．，Ｃｏｎｄｕｃｔｉｎｇ Ｐｏｌ
ｙｍｅｒｓ．，１０５（１９８７）に示す方法によりポ
リアニリンを合成した。 実施例１ ポリアニリン０．４５ｇ、昭和電工製ポリフッ化ビニリ
デン０．０５ｇを１０ｍｌのｎ−メチルピロリドンに溶
解した。この溶液をＳＵＳ３０４基板に塗布した後、１
７０℃で加熱し、ｎ−メチルピロリドンを除去した。Ｓ
ＵＳ３０４基板上には均質なポリアニリン／ポリフッ化
ビニリデン組成物フィルムが得られた。 実施例２ ポリアニリン０．３ｇ、昭和電工製ポリフッ化ビニリデ
ン０．２ｇを１０ｍｌのｎ−メチルピロリドンに溶解し
た。この溶液をガラス基板に塗布した後、１７０℃で加
熱し、ｎ−メチルピロリドンを除去した。ガラス基板上
には均質なポリアニリン／ポリフッ化ビニリデン組成物
フィルムが得られた。 実施例３ ポリアニリン０．１ｇ、昭和電工製ポリフッ化ビニリデ
ン０．４ｇを１０ｍｌのジメチルホルムアミドに溶解し
た。この溶液をアルミニウム基板に塗布した後、１７０
℃で加熱し、ジメチルホルムアミドを除去した。アルミ
ニウム基板上には均質なポリアニリン／ポリフッ化ビニ
リデン組成物フィルムが得られた。Production of polyaniline A. from ammonium persulfate and hydrochloric acid. G. MacDiar
mid et al. , Conducting Pol
ymers. , 105 (1987) to synthesize polyaniline. Example 1 0.45 g of polyaniline and 0.05 g of polyvinylidene fluoride manufactured by Showa Denko were dissolved in 10 ml of n-methylpyrrolidone. After applying this solution to the SUS304 substrate, 1
It heated at 70 degreeC and removed n-methyl pyrrolidone. S
A homogeneous polyaniline / polyvinylidene fluoride composition film was obtained on a US304 substrate. Example 2 0.3 g of polyaniline and 0.2 g of polyvinylidene fluoride manufactured by Showa Denko were dissolved in 10 ml of n-methylpyrrolidone. After applying this solution to a glass substrate, it was heated at 170 ° C. to remove n-methylpyrrolidone. A homogeneous polyaniline / polyvinylidene fluoride composition film was obtained on the glass substrate. Example 3 0.1 g of polyaniline and 0.4 g of polyvinylidene fluoride manufactured by Showa Denko were dissolved in 10 ml of dimethylformamide. After applying this solution to an aluminum substrate, 170
Heated at ° C to remove dimethylformamide. A homogeneous polyaniline / polyvinylidene fluoride composition film was obtained on an aluminum substrate.
【００１６】実施例４ 実施例１で製造したポリアニリン／ポリフッ化ビニリデ
ン組成物フィルムを１Ｍ過塩素酸ＨＣｌＯ4水溶液中に
１２時間浸漬した。洗浄、乾燥後、電気伝導度を測定し
たところ１Ｓ／ｃｍであった。 実施例５ 実施例２で製造したポリアニリン／ポリフッ化ビニリデ
ン組成物フィルムを１Ｍ硫酸水溶液中に１２時間浸漬し
た。洗浄、乾燥後、電気伝導度を測定したところ０．４
Ｓ／ｃｍであった。 実施例６ ポリアニリン０．４５ｇ、昭和電工製ポリフッ化ビニリ
デン０．０５ｇを５０ｍＭテトラシアノキノジメタン
（ＴＣＮＱ）を溶解させた１０ｍｌのｎ−メチルピロリ
ドンに溶解した。この溶液をＳＵＳ３０４基板に塗布し
た後、１７０℃で加熱し、ｎ−メチルピロリドンを除去
した。ＳＵＳ３０４基板上には均質なポリアニリン／ポ
リフッ化ビニリデン組成物フィルムが得られた。この組
成物フィルムの電気伝導度を測定したところ２×１０-4
Ｓ／ｃｍであった。Example 4 The polyaniline / polyvinylidene fluoride composition film prepared in Example 1 was immersed in a 1M aqueous solution of HClO 4 perchlorate for 12 hours. After washing and drying, the electric conductivity was measured and found to be 1 S / cm. Example 5 The polyaniline / polyvinylidene fluoride composition film produced in Example 2 was immersed in a 1M sulfuric acid aqueous solution for 12 hours. After washing and drying, the electric conductivity was measured and found to be 0.4.
It was S / cm. Example 6 0.45 g of polyaniline and 0.05 g of polyvinylidene fluoride manufactured by Showa Denko were dissolved in 10 ml of n-methylpyrrolidone in which 50 mM tetracyanoquinodimethane (TCNQ) was dissolved. After applying this solution to a SUS304 substrate, it was heated at 170 ° C. to remove n-methylpyrrolidone. A homogeneous polyaniline / polyvinylidene fluoride composition film was obtained on the SUS304 substrate. When the electric conductivity of this composition film was measured, it was 2 × 10 −4.
It was S / cm.
【００１７】実施例７ ポリアニリン０．３ｇ、昭和電工製ポリフッ化ビニリデ
ン０．２ｇを１０ｍｌのｎ−メチルピロリドンに溶解し
た。この溶液をマグネチックスターラーで撹拌している
５００ｍｌの水中に投入した。沈殿物を濾過、乾燥を行
い均質なポリアニリン／ポリフッ化ビニリデン組成物粉
末が得られた。この粉体を１Ｍ硫酸水溶液中に１２時間
浸漬した。洗浄乾燥後、２ｔ／ｃｍ2 のプレスにより成
型体を得た。この成型体の電気伝導度は０．３Ｓ／ｃｍ
であった。Example 7 0.3 g of polyaniline and 0.2 g of polyvinylidene fluoride manufactured by Showa Denko were dissolved in 10 ml of n-methylpyrrolidone. This solution was put into 500 ml of water which was stirred with a magnetic stirrer. The precipitate was filtered and dried to obtain a homogeneous polyaniline / polyvinylidene fluoride composition powder. This powder was immersed in a 1M sulfuric acid aqueous solution for 12 hours. After washing and drying, a molded product was obtained by pressing at 2 t / cm 2 . The electric conductivity of this molded body is 0.3 S / cm
Met.
【００１８】実施例８ ＭｎＯ2とＬｉＮＯ3をモル比７：３で混合し４００℃で
焼成したＭｎ−Ｌｉ複合酸化物を１．２ｇ、ポリアニリ
ン０．２ｇ、昭和電工製ポリフッ化ビニリデン０．２ｇ
を５０ｍＭテトラシアノキノジメタン（ＴＣＮＱ）を溶
解させた１０ｍｌのｎ−メチルピロリドンに混合し、マ
グネチックスターラーで撹拌し、ＳＵＳ３０４基板に塗
布した後、１７０℃で加熱し、ｎ−メチルピロリドンを
除去し、二次電池用正極を作製した。負極にＬｉを用い
電解液に１モルＬｉＣｌＯ4／プロピレンカーボネート
溶液を用いて二次電池特性を測定した。なお充放電は２
〜３．７Ｖの電圧範囲で０．２ｍＡ／ｃｍ2で行ったと
ころ正極電極重量あたり１５９ｍＡｈ／ｇの放電容量が
得られ、１００回以上のサイクル寿命が得られた。 実施例９ 実施例８においてＭｎ−Ｌｉ複合酸化物の代わりにＶ2
Ｏ5を用いる以外は実施例８と同様にして二次電池用正
極を作製し、二次電池特性を評価した。１６１ｍＡｈ／
ｇの放電容量が得られ、１００回以上のサイクル寿命が
得られた。Example 8 1.2 g of Mn-Li composite oxide obtained by mixing MnO 2 and LiNO 3 at a molar ratio of 7: 3 and calcined at 400 ° C., 0.2 g of polyaniline, 0.2 g of polyvinylidene fluoride manufactured by Showa Denko.
Was mixed with 10 ml of n-methylpyrrolidone in which 50 mM tetracyanoquinodimethane (TCNQ) was dissolved, stirred with a magnetic stirrer, applied on a SUS304 substrate, and then heated at 170 ° C. to remove n-methylpyrrolidone. Then, a positive electrode for a secondary battery was produced. Secondary battery characteristics were measured using Li as the negative electrode and a 1 mol LiClO 4 / propylene carbonate solution as the electrolytic solution. Charge and discharge is 2
When carried out at 0.2 mA / cm 2 in a voltage range of up to 3.7 V, a discharge capacity of 159 mAh / g per positive electrode weight was obtained, and a cycle life of 100 times or more was obtained. Example 9 In Example 8, V 2 was used instead of the Mn—Li composite oxide.
A positive electrode for a secondary battery was produced in the same manner as in Example 8 except that O 5 was used, and the characteristics of the secondary battery were evaluated. 161mAh /
A discharge capacity of g was obtained, and a cycle life of 100 times or more was obtained.
【００１９】実施例１０ ポリアニリン０．５ｇ、ポリフッ化ビニリデン０．５ｇ
を１０ｍｌのｎ−メチルピロリドンに溶解した。この溶
液を直径３ｃｍのシャーレに流し込み１７０℃で加熱
し、ｎ−メチルピロリドンを除去し厚さ３００μｍ、直
径３ｃｍのフィルムを得た。このフィルムを水中に１０
日間放置後乾燥を行ったところ、厚さ２８０μｍ、直径
２．７ｃｍで変形は少なかった。このフィルムを１Ｎ−
ＨＢＦ4水溶液中に１２時間浸漬した。乾燥後のフィル
ムは厚さ３０５μｍ、直径３．１ｃｍ、導電率７×１０
-2Ｓ／ｃｍであった。 比較例 ポリアニリン１ｇを１０ｍｌのｎ−メチルピロリドンに
溶解した。この溶液を直径３ｃｍのシャーレに流し込み
１７０℃で加熱し、ｎ−メチルピロリドンを除去し厚さ
３００μｍ、直径３ｃｍのフィルムを得た。このフイル
ムを水中に１０日間放置後乾燥を行ったところ厚さ１２
０μｍ、直径１．４ｃｍで変形は非常に大きかった。Example 10 0.5 g of polyaniline and 0.5 g of polyvinylidene fluoride
Was dissolved in 10 ml of n-methylpyrrolidone. This solution was poured into a petri dish having a diameter of 3 cm and heated at 170 ° C. to remove n-methylpyrrolidone to obtain a film having a thickness of 300 μm and a diameter of 3 cm. 10 this film in water
When it was dried after being left for one day, the thickness was 280 μm and the diameter was 2.7 cm, and the deformation was small. This film is 1N-
It was immersed in an HBF 4 aqueous solution for 12 hours. The dried film has a thickness of 305 μm, a diameter of 3.1 cm, and a conductivity of 7 × 10.
It was -2 S / cm. Comparative Example 1 g of polyaniline was dissolved in 10 ml of n-methylpyrrolidone. This solution was poured into a petri dish having a diameter of 3 cm and heated at 170 ° C. to remove n-methylpyrrolidone to obtain a film having a thickness of 300 μm and a diameter of 3 cm. This film was left in water for 10 days and then dried to obtain a thickness of 12
The deformation was very large at 0 μm and a diameter of 1.4 cm.
【００２０】[0020]
【効果】本発明により、ポリフッ化ビニリデンを含有す
る新規な導電性組成物を提供することができた。この組
成物は、導電性でありながら結着性を有することから電
極形成用結着剤として有用であり、とくにポリアニリン
と併用した組成物を結着剤として使用した場合には、ポ
リアニリンの特性を生かしつつ、ポリアニリンの強度と
接着性を改善することができた。また、本発明組成物を
用いて作った正極を使用した電池は、電流密度が高く、
サイクル寿命が長いという特色を発揮した。[Effect] According to the present invention, a novel conductive composition containing polyvinylidene fluoride can be provided. This composition is useful as an electrode-forming binder because it is electrically conductive but has a binding property. In particular, when a composition used in combination with polyaniline is used as a binder, the properties of polyaniline are improved. It was possible to improve the strength and adhesion of polyaniline while making the best use of it. Further, the battery using the positive electrode made using the composition of the present invention has a high current density,
It has the characteristic of long cycle life.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 9/02 ＪＡＱ 7415−4Ｊ Ｈ０１Ｍ 4/02 Ｃ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C09J 9/02 JAQ 7415-4J H01M 4/02 C
Claims (7)
リデンからなる導電性組成物。1. A conductive composition comprising a soluble conductive polymer and polyvinylidene fluoride.
である請求項１記載の導電性組成物。2. The conductive composition according to claim 1, wherein the soluble conductive polymer is polyaniline.
錯体を形成している請求項２記載の導電性組成物。3. The conductive composition according to claim 2, wherein the polyaniline forms a complex with an organic acceptor.
１、２または３記載の導電性組成物。4. The conductive composition according to claim 1, 2 or 3, wherein the composition is in the form of a film.
リデン双方を可溶な溶媒に均一に溶解した後、溶媒を除
去することを特徴とする導電性組成物の製造方法。5. A method for producing a conductive composition, which comprises uniformly dissolving both a soluble conductive polymer and polyvinylidene fluoride in a soluble solvent and then removing the solvent.
りなる電極形成用結着剤。6. A binder for forming an electrode, which comprises the composition according to claim 1, 2, or 3.
た電極を正極として使用したことを特徴とする電池。7. A battery using the electrode formed by using the binder according to claim 6 as a positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4296396A JPH06124708A (en) | 1992-10-08 | 1992-10-08 | Conductive composition containing polyvinylidene fluoride and battery using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4296396A JPH06124708A (en) | 1992-10-08 | 1992-10-08 | Conductive composition containing polyvinylidene fluoride and battery using the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06124708A true JPH06124708A (en) | 1994-05-06 |
Family
ID=17833006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4296396A Pending JPH06124708A (en) | 1992-10-08 | 1992-10-08 | Conductive composition containing polyvinylidene fluoride and battery using the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06124708A (en) |
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| WO2004064079A1 (en) * | 2003-01-06 | 2004-07-29 | E. I. Du Pont De Nemours And Company | Electrically conductive polymer films |
| WO2004091017A1 (en) * | 2003-04-07 | 2004-10-21 | Lg Chem Ltd. | The constitution of the dispersant in the preparation of the electrode active material slurry and the use of the dispersant |
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-
1992
- 1992-10-08 JP JP4296396A patent/JPH06124708A/en active Pending
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| US5716550A (en) * | 1995-08-10 | 1998-02-10 | Eastman Kodak Company | Electrically conductive composition and elements containing solubilized polyaniline complex and solvent mixture |
| US5910385A (en) * | 1995-08-10 | 1999-06-08 | Eastman Kodak Company | Electrically conductive composition and elements containing solubilized polyaniline complex |
| EP0758671A3 (en) * | 1995-08-10 | 1997-02-26 | Eastman Kodak Company | Electrically conductive composition and elements containing solubilized polyaniline complex |
| US6248474B1 (en) * | 1997-11-04 | 2001-06-19 | Nec Corporation | Composite electrode for secondary battery and production method thereof |
| KR100463179B1 (en) * | 2001-09-26 | 2004-12-23 | 삼성에스디아이 주식회사 | Preparation method for materials for electrodes of lithium secondary battery and lithium secondary battery |
| US7192536B2 (en) | 2003-01-06 | 2007-03-20 | E. I. Du Pont De Nemours And Company | Electrically conductive polymer films and process for making same |
| US6932921B2 (en) | 2003-01-06 | 2005-08-23 | E. I. Du Pont De Nemours And Company | Electrically conductive polymer films |
| WO2004064079A1 (en) * | 2003-01-06 | 2004-07-29 | E. I. Du Pont De Nemours And Company | Electrically conductive polymer films |
| WO2004091017A1 (en) * | 2003-04-07 | 2004-10-21 | Lg Chem Ltd. | The constitution of the dispersant in the preparation of the electrode active material slurry and the use of the dispersant |
| CN100409470C (en) * | 2003-04-07 | 2008-08-06 | 株式会社Lg化学 | The constitution of the dispersant in the preparation of the electrode active material slurry and the use of the dispersant |
| US7862929B2 (en) | 2003-04-07 | 2011-01-04 | Lg Chem, Ltd. | Constitution of the dispersant in the preparation of the electrode active material slurry and the use of the dispersant |
| JP2014194951A (en) * | 2009-04-02 | 2014-10-09 | Plextronics Inc | Binder for lithium ion secondary battery positive electrode, and positive electrode material |
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