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KR840007487A - Method for producing a polymer of electrically conductive polypyrrole and pyrrole and battery - Google Patents

Method for producing a polymer of electrically conductive polypyrrole and pyrrole and battery Download PDF

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KR840007487A
KR840007487A KR1019840000283A KR840000283A KR840007487A KR 840007487 A KR840007487 A KR 840007487A KR 1019840000283 A KR1019840000283 A KR 1019840000283A KR 840000283 A KR840000283 A KR 840000283A KR 840007487 A KR840007487 A KR 840007487A
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pyrrole
polymer
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electrically conductive
compound
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엠. 저어디스(외 2) 해롤드
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도날드 엘. 머핀
루브리졸 엔터프라이즈 인코오퍼레이티드
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

내용 없음.No content.

Description

전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법 및 전지Method for producing a polymer of electrically conductive polypyrrole and pyrrole and battery

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

제1도는 본 발명의 리듐전지(lithium cell)를 도시한 횡단면 입면예시도.1 is a cross-sectional elevation view showing a lithium cell of the present invention.

제2도는 본 발명의 다른 실시구체 양태를 도시한 전지의 횡단면 입면예시도.2 is a cross-sectional elevation view of a cell showing another embodiment of the present invention.

제3도는 본 발명의 다른 실시 구체 양태를 도시한 전기화학적 에너지 축전지의 투시 예시도.3 is a perspective view of an electrochemical energy storage battery showing another embodiment of the present invention.

제4도는 제3도에 도시된 전지의 횡단면 입면도.4 is a cross-sectional elevation view of the cell shown in FIG.

제5도는 본 발명의 다른 실시 구체 양태를 도시한 전기화학적 에너지 축전지의 횡단면 입면 예시도.5 is a cross-sectional elevation view illustrating an electrochemical energy storage battery showing another embodiment of the present invention.

Claims (41)

다음 단계로 이루어지는 전해조의 전기전도 표면에서 또는 피롤을 함유하는 혼성 중합화할 수 있는 혼합물의 전기 중합반응으로 되는 전기전도 폴리 피롤과 피롤의 혼성 중합체의 제조방법. A. 적어도 하나의 액체와 적어도 하나의 섞이지 아니하는 액체 또는 가스 또는 미세하게 쪼개진 고체 입자로 이루어지며, 피롤 또는 피롤을 함유하는 혼성 중합화할 수 있는 혼합물이 이 액체들중에 하나이거나 또는 이 액체중에 용해되어 있는 것으로 이루어진 전해조에 전기전도 표면을 담그고, B. 전기 전도표면에 피롤 또는 피롤을 함유하는 혼성 중합화할 수 있는 혼합물을 전기 중합하는 데 충분한 전압으로 전류를 전해도에 통과시킨다.A method for producing an interpolymer of electrically conductive polypyrrole and pyrrole, which is subjected to an electropolymerization reaction of an interpolymerizable mixture containing pyrrole or on an electrically conductive surface of an electrolytic cell comprising the following steps. A. A hybridizable polymerizable mixture comprising at least one liquid and at least one non-mixing liquid or gas or finely divided solid particles and containing pyrrole or pyrrole is one of these liquids or dissolved in the liquid The electroconductive surface is immersed in an electrolyzer consisting of a single cell, and B. A current is passed through the electrolytic cell at a voltage sufficient to electropolymerize a pyrrole or a pyropolymerizable mixture containing pyrrole on the electrically conductive surface. 제1항에 있어서 전류가 직류 또는 교류인 전기전도 폴리피롤과 피롤의 혼성중합체의 제조방법.The method for producing an interpolymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the current is direct current or alternating current. 제1항에 있어서 전류가 전해조를 통과하는 동안 전해조가 교반되는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1 wherein the electrolytic cell is stirred while the current passes through the electrolytic cell. 제1항에 있어서 폴리피롤 또는 혼성 중합체가 전도 표면에 부착되는 전기 전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1 wherein the polypyrrole or interpolymer is attached to the conductive surface. 제1항에 있어서 피롤 또는 피롤의 혼성 중합체가 전도 표면에서 분말로 형성되어 전해조내에 분산되는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the pyrrole or pyrrole interpolymer is formed into a powder on the conductive surface and dispersed in the electrolytic cell. 제1항에 있어서 전해조가 피롤, 물 및 물에 섞이지 아니하는 유기 희석제로 이루어지는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method for producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the electrolytic cell is made of pyrrole, water and an organic diluent which is not mixed with water. 제1항에 있어서 전해조가 또한 에멀션제를 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1 wherein the electrolytic cell also comprises an emulsion as an electrically conductive polypyrrole and pyrrole interpolymer. 제1항에 있어서 전류가 전해조를 통과할때 전해조가 약 15℃에서 50℃로 유지되는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1, wherein the electrolytic cell is maintained at about 15 ° C. to 50 ° C. when current passes through the electrolytic cell. 제1항에 있어서 폴리피롤 또는 피롤의 혼성 중합체에 혼합되어 있으며 환원시에 평균 이온 전달율이 0.1이하인 것이 특징인 저 이동성 음이온을 전해조가 또한 함유하고 있는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method for producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the electrolytic cell also contains a low mobility anion, which is mixed with the polypyrrole or pyrrole interpolymer and has an average ion transfer rate of 0.1 or less upon reduction. 제1항에 있어서 전기전도 폴리피롤 또는 피롤의 혼성 중합체를 가열처리하여 이 화합물의 전기 화학적 축적 용량을 증가시키는 단계를 가진 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1, wherein the step of heat treating the electrically conductive polypyrrole or pyrrole hybrid polymer to increase the electrochemical accumulation capacity of the compound. 제9항에 잇어서 전해조내의 음이온이 유기 황산염 또는 술폰산염으로부터 유도된 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.10. A process for producing a hybrid polymer of electrically conductive polypyrrole and pyrrole in which the anion in the electrolytic cell is derived from organic sulfates or sulfonates. 제11항에 있어서 황산염 또는 술폰산염이 아릴, 아릴알킬, 알카릴 또는 폴리 올레핀이 황산염 또는 술폰산염이며, 각각이 1개 또는 2 이상의 음이온 부위를 가지고 있는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.12. The method for producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 11, wherein the sulfate or sulfonate is aryl, arylalkyl, alkaryl or polyolefin is sulfate or sulfonate, each having one or two anion sites. . 제9항에 있어서 음이온들의 5가의 인산 화합물로부터 유도되는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.10. The method of producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 9, derived from a pentavalent phosphate compound of anions. 제1항에 있어서 전해조가 또한 가소제를 함유하는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the electrolytic cell also contains a plasticizer. 제1항에 있어서 전해조가 산화 환원제를 함유하는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method for producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the electrolytic cell contains a redox agent. 제1항에 있어서 전해조가 또한 중성 또는 이온 표면활성 화합물을 함유하는 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of producing a hybrid polymer of electrically conductive polypyrrole and pyrrole according to claim 1, wherein the electrolytic cell also contains a neutral or ionic surface active compound. 제1항에 있어서 폴리피롤 또는 피롤의 혼성 중합체가 약 0.01gcm-3에서 이 폴리피롤 또는 혼성 중합체의 부피밀도 까지에 이르는 겉보기 밀도와 이 화합물의 부피밀도를 가진 매끈한 막 표면적의 적어도 2배의 표면적을 갖는 것이 특징인 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.The method of claim 1 wherein the polypyrrole or pyrrole interpolymer has an apparent density ranging from about 0.01 gcm −3 to the bulk density of the polypyrrole or interpolymer and at least twice the surface area of the smooth membrane surface area having the bulk density of the compound. Method for producing a conductive polymer of electrically conductive polypyrrole and pyrrole characterized in that. 제17항에 있어서 앞에서 말한 폴리피폴 또는 혼성중합체의 밀도가 약 0.2gcm-3에서 약 0.8gcm-3인 전기전도 폴리피롤과 피롤의 혼성 중합체의 제조방법.18. The method of claim 17 wherein the polypipol or copolymer described above has a density of about 0.2 gcm -3 to about 0.8 gcm -3 . 중합체 전극이 전기 중합화된 폴리피롤 또는 피롤의 혼성 중합체로된 다공질의 전기전도 화합물로 이루어지고, 이 화합물은 약 0.01gcm-3에서 이 폴리피롤 또는 피롤의 혼성 중합체의 부피밀도 까지에 이르는 겉보기 밀도와 이 화합물의 부피밀도를 가진 매끄러운 막 표면적의 적어도 2배의 표면적이 특징인 중합체 전극으로 이루어지는 전지.The polymer electrode consists of a porous electrically conductive compound of an electropolymerized polypyrrole or pyrrole interpolymer, the compound having an apparent density ranging from about 0.01 gcm -3 to the bulk density of the polypyrrole or pyrrole interpolymer A cell consisting of a polymer electrode characterized by at least twice the surface area of a smooth membrane surface area having a bulk density of the compound. 제19항에 있어서 중합체 전극이 적어도 2개의 다공질 전지전도 합성화합물로 되며 이중에서 적어도 한개는 다공질 전기전도 화합물로 이루어지는 전지.20. A battery according to claim 19, wherein the polymer electrode consists of at least two porous cell conducting synthetic compounds, at least one of which consists of a porous electric conducting compound. 제19항에 있어서 화합물의 밀도가 약 0.2gcm-3에서 약 0.3cm-3인 전지.The cell of claim 19, wherein the compound has a density of about 0.2 gcm −3 to about 0.3 cm −3 . 제19항에 있어서, 화합물이 환원시에 평균 이온 전달율이 약 0.1이하인 것이 특징인 저 이동성 음이온을 또한 함유하고 있는 전지.20. The battery of claim 19, wherein the compound also contains a low mobility anion characterized in that the average ion transfer rate upon reduction is about 0.1 or less. 제19항에 있어서 화합물이 가열처리되어 이 화합물이 전기 화학적 축적용량을 증가시키는 전지.The cell of claim 19, wherein the compound is heat treated to increase the electrochemical storage capacity. 제22항에 있어서 음이온이 유기 황산염 또는 술폰산염으로부터 유도된 전지.The cell of claim 22, wherein the anion is derived from an organic sulfate or sulfonate. 제24항에 있어서 황산염 또는 술폰산염이 알킬, 아릴, 아릴알킬, 알카릴 또는 폴리올레핀의 황산염 또는 술폰산염이며 각각이 1개 또는 그 이상의 음이온 부위를 가지고 있는 전지.The cell of claim 24 wherein the sulfate or sulfonate is a sulfate or sulfonate of an alkyl, aryl, arylalkyl, alkaryl or polyolefin, each having one or more anion sites. 제24항에 있어서 음이온들이 알킬기에 적어도 4개의 탄소원자를 가지고 있는 알킬 황산염으로 부터 유도된 것인 전지.The cell of claim 24, wherein the anions are derived from alkyl sulfates having at least 4 carbon atoms in the alkyl group. 제26항에 있어서 황산염이 라우릴 황산염인 전지.The cell of claim 26, wherein the sulfate is lauryl sulfate. 제22항에 있어서 음이온들이 2가의 인산 화합물로 부터 유도된 전지.The cell of claim 22, wherein the anions are derived from a divalent phosphate compound. 제19항에 있어서 화합물이 적어도 한 개의 가소제를 또한 함유하고 있는 전지.The battery of claim 19, wherein the compound also contains at least one plasticizer. 제19항에 있어서 화합물이 산화환원제를 함유하는 전지.The battery of claim 19 wherein the compound contains a redox agent. 제19항에 있어서 중합체 전극이 양극으로되며 또 금속 음극과 분리기, 전해질로 이루어지는 전지.20. A battery according to claim 19, wherein the polymer electrode is an anode, and is made of a metal cathode, a separator, and an electrolyte. 제31항에 있어서 음극이 알칼리 금속, 알칼리토 금속, 또는 이 알칼리 금속 또는 알칼리토 금속의 합금으로 이루어지는 전지.The battery according to claim 31, wherein the negative electrode is made of an alkali metal, an alkaline earth metal, or an alloy of the alkali metal or alkaline earth metal. 제31항에 있어서 음극이 리듐, 나트륨, 칼륨, 마그네슘, 칼슘 또는 이들의 합금으로된 기중에서 선택된 물질로 이루어지는 전지.32. A battery according to claim 31, wherein the negative electrode is made of a material selected from the group consisting of lithium, sodium, potassium, magnesium, calcium or alloys thereof. 제19항에 있어서 화합물이 냉압되어 중합체 전극을 만드는 전지.The cell of claim 19 wherein the compound is cold pressed to form a polymer electrode. 제19항에 있어서 화합물이 결합제를 함유하며 이 화합물이 냉압되어 중합체 전극을 만드는 전지.The cell of claim 19, wherein the compound contains a binder and the compound is cold pressed to make a polymer electrode. 제31항에 있어서 전기 접촉기가 중합체 양극과 분리기 사이에 위치한 막(screen) 또는 그리드에 의해 중합체 양극에 만들어지는 전지.The cell of claim 31, wherein an electrical contactor is made at the polymer anode by a screen or grid positioned between the polymer anode and the separator. 제19항에 있어서 중합체 전극이 음극으로 되고 또한 분리기, 전해질, 및 또 하나의 다른 전극으로 이루어지는 전지로서 이 또 하나의 다른 전극은 이 중합체 음극보다 전기 화학적으로 좀더 양극을 띠는 것인 전지.20. A cell according to claim 19, wherein the polymer electrode is a negative electrode and consists of a separator, an electrolyte, and another other electrode, wherein this another electrode is more electrochemically more positive than the polymer negative electrode. 제37항에 있어서 전기 접촉기가 중합체 음극과 분리기 사이에 위치한 막 또는 그리드에 의해 중합체 음극에 만들어지는 전지.The cell of claim 37, wherein an electrical contactor is made at the polymer anode by a membrane or grid positioned between the polymer anode and the separator. 제19항에 있어서 중합체 전극이 중합체 음극 및 중합체 양극으로 이루어지며, 또한 분리기와 전해질로 이루어지는 전지.The battery according to claim 19, wherein the polymer electrode consists of a polymer negative electrode and a polymer positive electrode, and further comprises a separator and an electrolyte. 제39항에 있어서 중합체 양극이 지나친 방전으로 생기는 전지의 손상에 대해 강화된 저항 장벽을 제공하며 또는 이 중합체 음극이 지나친 하전으로 생기는 전지의 손상에 대한 강화된 저항 장벽을 제공하는 전지.40. A cell according to claim 39, wherein the polymer anode provides a reinforced resistance barrier against damage to the cell resulting from excessive discharge or the polymer anode provides a reinforced resistance barrier against damage to the cell caused by excessive charge. 제39항에 있어서 전기 접촉기가 중합체 양극과 분리기 사이에 위치한 막 또는 그리드에 의해 중합체 양극에 만들어지며/또는 전기 접촉기가 중합체 음극과 분리기 사이에 위치한 막 또는 그리드에 의해 음극으로 만들어지는 전지.40. The cell of claim 39, wherein the electrical contactor is made at the polymer anode by a membrane or grid positioned between the polymer anode and the separator and / or the electrical contactor is made at the cathode by a membrane or grid located between the polymer anode and the separator. ※ 참고사항:최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019840000283A 1983-01-24 1984-01-19 Method for producing a polymer of electrically conductive polypyrrole and pyrrole and battery KR840007487A (en)

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