JPS63181273A - Manufacture of cell - Google Patents
Manufacture of cellInfo
- Publication number
- JPS63181273A JPS63181273A JP62012272A JP1227287A JPS63181273A JP S63181273 A JPS63181273 A JP S63181273A JP 62012272 A JP62012272 A JP 62012272A JP 1227287 A JP1227287 A JP 1227287A JP S63181273 A JPS63181273 A JP S63181273A
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- electrolyte
- ion
- film
- electrolysis
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 53
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 description 11
- 239000002322 conducting polymer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002632 poly(dichlorophosphazene) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
Classifications
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、イオン伝導性高分子電解質中で電解重合して
得られた電子伝導性高分子とイオン伝導性高分子電解質
を正極および電解質隔膜として用いた電池の製造法に関
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of an electron conductive polymer obtained by electrolytic polymerization in an ion conductive polymer electrolyte and an ion conductive polymer electrolyte as a positive electrode and an electrolyte diaphragm. This paper relates to a method for manufacturing a battery used as a battery.
［従来技術およびその問題点］
従来より、電極として電子伝導性高分子を用いた電池が
知られている。この電池は、従来の二次電池に比較して
、軽量であるため、高エネルギー密度である利点を有し
ている。これに用いられる電子伝導性高分子材料として
ポリアセチレンがよく知られている。[Prior art and its problems] Batteries using electronically conductive polymers as electrodes have been known. This battery has the advantage of being lightweight and high energy density compared to conventional secondary batteries. Polyacetylene is well known as an electron conductive polymer material used for this purpose.
しかし、ポリアセチレンを電池の電極に用いた場合は、
自己放電性が大きく、また、充放電中に、ドーピングに
伴い、酸化により劣化するという欠点があった。However, when polyacetylene is used for battery electrodes,
It has a drawback that it has a large self-discharge property, and also deteriorates due to oxidation due to doping during charging and discharging.
そこで、最近、この欠点を除くため、電解重合法によっ
て得られた電子伝導性高分子１例えば、ポリピロール、
ポリチオフェン、ポリアニリン等やあるいはそれらの誘
導体を電極に用いて、上記の欠点のない電池が提案され
ている０例えば、特開昭６０−２１６４７０号では、電
子伝導性高分子材料を一方の電極として用いる一対の電
極と非本有機電解液とを有する電池であって、陽極に電
子伝導性高分子材料としてポリピロールを用い、負極に
アルカリ金属を用いることを特徴とする特池、および、
電解質を有機溶媒に溶かした電解液中にピロールを加え
、得られた溶液に一対の導電性基板を浸漬し、電解重合
により導電性基板上にポリピロールを形成した後、得ら
れたポリピロールを陽極とし、アルカリ金属を負極とし
、電解液と接触させることを特徴とする電池の製造法、
について述べられている。Recently, in order to eliminate this drawback, electronic conductive polymers 1 obtained by electrolytic polymerization, such as polypyrrole,
Batteries free from the above-mentioned drawbacks have been proposed using polythiophene, polyaniline, etc. or their derivatives as electrodes. A battery having a pair of electrodes and a non-organic electrolyte, characterized in that the anode uses polypyrrole as an electron-conductive polymer material and the anode uses an alkali metal, and
Pyrrole is added to an electrolytic solution in which an electrolyte is dissolved in an organic solvent, a pair of conductive substrates is immersed in the resulting solution, polypyrrole is formed on the conductive substrate by electrolytic polymerization, and the resulting polypyrrole is used as an anode. , a method for producing a battery characterized by using an alkali metal as a negative electrode and bringing it into contact with an electrolyte;
is mentioned.
しかしながら、液体電解質を用いているため、長期の使
用の間に電池外部への液もれ、電解質溶媒の揮発などの
ため、長期信頼性の問題がある。However, since a liquid electrolyte is used, there are problems with long-term reliability due to liquid leakage to the outside of the battery and volatilization of the electrolyte solvent during long-term use.
この問題を解決する方法として、液体電解質の代わりに
、固体電解質を用いる方法が提案されている。しかし、
この場合は、固体同士を積層するため、電極と固体電解
質との界面の接触が、ミクロ的にみれば不完全であり、
組み立てた電池の内部抵抗が高くなる。また、ｍ層する
工程が煩雑であり、電子伝導性高分子に機械的な強度が
必要など１種々問題がある。As a method to solve this problem, a method using a solid electrolyte instead of a liquid electrolyte has been proposed. but,
In this case, since the solids are stacked together, contact at the interface between the electrode and the solid electrolyte is incomplete from a microscopic perspective.
The internal resistance of the assembled battery increases. Further, there are various problems such as the step of forming m layers is complicated and the electronic conductive polymer needs to have mechanical strength.
本発明の目的は、従来からの、電極として電子伝導性高
分子を用いた電池の欠点を改良し、優れた特性を有する
電池を提供するものである。An object of the present invention is to improve the drawbacks of conventional batteries using electronically conductive polymers as electrodes and to provide a battery with excellent characteristics.
［問題点を解決するための手段］
本発明は、イオン伝導性高分子電解質中に原料モノマー
を含浸させ、その両側に電極をはさみ、電解重合により
イオン伝導性高分子電解質の表面に電子伝導性高分子を
形成させて得られた、電子伝導性高分子とイオン伝導性
高分子電解質の複合フィルムのうち、電子伝導性高分子
を正極、およびイオン伝導性高分子電解質を電解質隔膜
として用いることを特徴とする電池の製造法を提供する
ことにより、前記目的を達成したものである。[Means for Solving the Problems] The present invention involves impregnating raw material monomers into an ion-conducting polymer electrolyte, sandwiching electrodes on both sides of the material, and applying electrolytic polymerization to the surface of the ion-conducting polymer electrolyte. Among the composite films of an electron conductive polymer and an ion conductive polymer electrolyte obtained by forming a polymer, it is possible to use the electron conductive polymer as a positive electrode and the ion conductive polymer electrolyte as an electrolyte diaphragm. The above object has been achieved by providing a method for manufacturing a battery with characteristics.
本発明の電解重合法により形成した電子伝導性高分子は
、正電極側ではなく、イオン伝導性高分子電解質側に成
長することに、特徴を有している。すなわち、電解重合
が終わった後、上記の正電極とイオン伝導性高分子電解
質フィルムをはがすと、電子伝導性高分子とイオン伝導
性高分子電解質の複合膜が得られる。The electron conductive polymer formed by the electrolytic polymerization method of the present invention is characterized in that it grows not on the positive electrode side but on the ion conductive polymer electrolyte side. That is, when the positive electrode and the ion-conducting polymer electrolyte film are peeled off after the electrolytic polymerization is completed, a composite membrane of the electron-conducting polymer and the ion-conducting polymer electrolyte is obtained.
本発明によって得られた電子伝導性高分子は、イオン伝
導性高分子電解質フィルムと一体化しているため、十分
な機械的強度を有しており、電池セルを組み立てるのに
、取り扱いが非常に簡単になる。また、従来の別々に形
成された電子伝導体とイオン伝導性高分子電解質を積層
する場合に比べて、界面抵抗が小さく電池特性が向上す
る利点を有している。Since the electronically conductive polymer obtained by the present invention is integrated with an ionically conductive polymer electrolyte film, it has sufficient mechanical strength and is extremely easy to handle when assembling battery cells. become. Furthermore, compared to the conventional stacking of separately formed electron conductors and ion conductive polymer electrolytes, this method has the advantage of lower interfacial resistance and improved battery characteristics.
また、電池の構成成分がすべて固体であり、液体電解質
を用いるに比べ液もれなどの問題が無く、電池の封口が
簡単であり、長期保存性に優れている。In addition, all of the constituent components of the battery are solid, so there are no problems such as leakage compared to using a liquid electrolyte, the battery can be easily sealed, and it has excellent long-term storage stability.
本発明において、イオン伝導性高分子電解質は、無機イ
オン塩と、その無機イオン塩を解離固溶化できる有機高
分子とから形成される。In the present invention, the ion conductive polymer electrolyte is formed from an inorganic ionic salt and an organic polymer capable of dissociating and converting the inorganic ionic salt into a solid solution.
本発明において、無機イオン塩としては、ＬｉＢＦ４
、ＬｉＣｌＯ４、ＬｉＢｒ。In the present invention, as the inorganic ionic salt, LiBF4
, LiClO4, LiBr.
ＢｕＮａ ＣｌＯ４、ＢｕＮ４ ＢＦ４ 。BuNa ClO4, BuN4 BF4.
ＮａＣＪ１０４ 、ＮａＢＦ４ 、ＫＣＪＬＯ４などを
挙げることができる。Examples include NaCJ104, NaBF4, KCJLO4, and the like.
また、ここで用いられる有機高分子としては、ポリエチ
レンオキシド、ポリプロピレンオキシド、ポリエチレン
スルフィド、ポリ−β−プロピオラクトン、ポリエチレ
ンサクシネートなどの高分子、あるいは、ポリエチレン
グリコールメタクリレートを重合した高分子、ポリエチ
レンオキシド付加グリセリンをジイソシアネートで架橋
して得られる高分子、ポリエチレンオキシドを側鎖に有
するポリシロキサン及びその架橋高分子、ポリ（ジクロ
ロフォスフアゼン）と２−（２−メトキシエトキシ）エ
タノールのナトリウム塩との反応で得られる高分子、な
どが挙げられる。また、１；記の有機高分子にイオン伝
導性を増大させるために、機械的強度を損なわない範囲
で、プロピレンカーボネート、アセトニトリルなどの有
機溶媒、あるいは低分子量ポリエチレングリコールを含
有させてもよい。In addition, the organic polymers used here include polymers such as polyethylene oxide, polypropylene oxide, polyethylene sulfide, poly-β-propiolactone, and polyethylene succinate, or polymers obtained by polymerizing polyethylene glycol methacrylate, and polyethylene oxide. Polymers obtained by crosslinking added glycerin with diisocyanate, polysiloxanes having polyethylene oxide in their side chains, and crosslinked polymers thereof, poly(dichlorophosphazene) and sodium salt of 2-(2-methoxyethoxy)ethanol. Examples include polymers obtained by reaction. Further, in order to increase the ionic conductivity of the organic polymer described in 1., organic solvents such as propylene carbonate and acetonitrile, or low molecular weight polyethylene glycol may be contained within a range that does not impair mechanical strength.
上記無機イオン塩の含有量としては、有機高分子に対し
て、０．０１〜５０ｗｔ％、好ましくは０．１〜３０ｗ
ｔ％の範囲が好ましい、上記無機イオン填の含有量が多
すぎると過剰の無機イオン塩が解離固溶化せず単に混在
するのみとなり、イオン伝導性は低下する。また、含有
量が少なすぎても、電荷キャリアーである解離イオンの
数が少なくなり、イオン伝導性は低下する。イオン伝導
性の低下は、電解重合および電池特性に悪影響をあたえ
る。The content of the inorganic ionic salt is 0.01 to 50 wt%, preferably 0.1 to 30 wt%, based on the organic polymer.
If the content of the inorganic ion filler, which is preferably in the range of t%, is too large, the excess inorganic ion salt will not be dissociated into a solid solution but will simply be mixed together, resulting in a decrease in ionic conductivity. Furthermore, if the content is too low, the number of dissociated ions that are charge carriers will decrease, resulting in a decrease in ionic conductivity. A decrease in ionic conductivity adversely affects electrolytic polymerization and battery characteristics.
イオン伝導性高分子電解質のフィルムの作成法としては
、上記の有機高分子と無機イオン塩との良溶媒で均一溶
液とし、均質な厚さになる様に塗布した後に溶媒を蒸発
除去してフィルムを作成する方法、また、有機高分子と
無機イオン塩の液状組成物を塗布した後に加熱あるいは
活性光線の照射などにより架橋硬化してフィルムを作成
する方法などがある。The method for making an ion-conductive polymer electrolyte film is to make a homogeneous solution of the above organic polymer and inorganic ionic salt in a good solvent, apply it to a uniform thickness, and then evaporate the solvent to form a film. There is also a method in which a liquid composition of an organic polymer and an inorganic ionic salt is applied and then cross-linked and cured by heating or irradiation with actinic rays to form a film.
本発明における、原料モノマーとしては、ピロール、Ｎ
−７リールピロール、Ｎ−アルキルピロールなどのピロ
ール系化合物、チオフェン、３〜アルキルチオフエンな
どのチオフェン化合物、あるいは、アニリンなどを挙げ
ることができる。In the present invention, raw material monomers include pyrrole, N
Examples include pyrrole compounds such as -7lylpyrrole and N-alkylpyrrole, thiophene compounds such as thiophene and 3-alkylthiophene, and aniline.
これらのモノマーは、単独でも、混合しても用いること
ができる。These monomers can be used alone or in combination.
原料モノマーの含浸量は、イオン伝導性高分子電解質に
対して、０．０１〜５０ｗｔ％、好ましくは２〜４０ｗ
ｔ％である。上記モノマーの含浸量が、上記の範囲より
も小さい場合は、ポリマー電池に適した表面積の大きな
電解重合膜の形成が困難であり、上記範囲よりも大きい
場合は、イオン伝導性高分子電解質の機械的性質が低下
して実用上好ましくない。The amount of raw material monomer impregnated is 0.01 to 50 wt%, preferably 2 to 40 wt%, based on the ion conductive polymer electrolyte.
t%. If the amount of the monomer impregnated is smaller than the above range, it will be difficult to form an electrolytic polymer membrane with a large surface area suitable for polymer batteries, and if it is larger than the above range, it will be difficult to form an electrolytic polymer membrane with a large surface area suitable for polymer batteries. This is not preferred in practice as the physical properties deteriorate.
上記のイオン伝導性高分子電解質のフィルムに、原料上
ツマ−を含浸させる方法としては、得に制限はないが、
例えば、フィルムに直接滴下し吸収させる方法、フィル
ムに気相で吸収させる方法などがある。There are no particular restrictions on the method of impregnating the film of the above-mentioned ion-conductive polymer electrolyte with the raw material, but
For example, there are a method of directly dropping it onto a film and absorbing it, and a method of letting the film absorb it in a gas phase.
上記のモノマーを含浸させたイオン伝導性高分子電解質
を用いて、モノマーを電解重合させる方法としては、イ
オン伝導性高分子電解質のフィルムを正負電極にはさみ
、該正負電極に直流電流を通電して、上記の該七ツマ−
を電解重合させて。A method for electrolytically polymerizing monomers using an ion-conducting polymer electrolyte impregnated with the above monomer is to sandwich a film of the ion-conducting polymer electrolyte between positive and negative electrodes and passing a direct current through the positive and negative electrodes. , the above-mentioned seven
is electrolytically polymerized.
正電極に接した高分子電解質フィルム面に、上記七ツマ
−の重合体膜を形成させる。The above seven-layer polymer film is formed on the surface of the polymer electrolyte film in contact with the positive electrode.
上記正電極としては、電解重合により酸化溶解、あるい
は不働態化を起こさない導電体であり、例えば、白金、
金、ニッケル、カーボン複合材。The positive electrode is a conductor that does not undergo oxidative dissolution or passivation through electrolytic polymerization, such as platinum,
Gold, nickel and carbon composite.
ＩＴＯガラスなどが挙げられる。また、負電極も上記と
同様に電解重合中に酸化溶解、不働態化を起こさない導
電体であり、白金、アルミニュウム。Examples include ITO glass. Similarly to the above, the negative electrode is also a conductor that does not undergo oxidative dissolution or passivation during electrolytic polymerization, such as platinum or aluminum.
鉄、銅、ニッケル、カーボン複合体、リチウム箔。Iron, copper, nickel, carbon composite, lithium foil.
ＩＴＯガラスなどが挙げられる。Examples include ITO glass.
本発明の電子伝導性高分子とイオン伝導性高分□子電解
質の複合膜を用いて、電池を組み立てるには、それぞれ
を、正極および電解質隔膜とし、さらに、正極集電体と
負極及び負極集電体を８Ｉ層する方法、あるいは、電解
重合で用いた正負電極をそのまま正負の集電体として用
いても良い。In order to assemble a battery using the composite membrane of an electron conductive polymer and an ion conductive polymer electrolyte of the present invention, each is used as a positive electrode and an electrolyte diaphragm, and further, a positive electrode current collector, a negative electrode, and a negative electrode collector are used. Alternatively, the positive and negative electrodes used in electrolytic polymerization may be used as positive and negative current collectors.
［本発明の効果］
本発明の製造法によれば、電子伝導性高分子とイオン伝
導性高分子電解質とが一体化したものが得られ、この両
者を積層したものに比べて界面抵抗が少なく電池特性の
よい電池が得られる。また、機械的性質がよく、電池セ
ルの組み立てが簡単等の効果がある。[Effects of the present invention] According to the manufacturing method of the present invention, a product in which an electronically conductive polymer and an ionically conductive polymer electrolyte are integrated can be obtained, and the interfacial resistance is lower than that of a laminated product of both. A battery with good battery characteristics can be obtained. In addition, it has good mechanical properties and has advantages such as easy assembly of battery cells.
［本発明の実施例］
（実施例）
メトキシポリエチレングリコールモノアクリレート （
新中村化学■製、ＡＭ−９０Ｇ）０．７５ｇ、ポリエチ
レングリコールジメタクリレート（新中村化学■製、９
Ｇ）０．２５ｇ。[Example of the present invention] (Example) Methoxypolyethylene glycol monoacrylate (
Shin Nakamura Chemical ■, AM-90G) 0.75 g, polyethylene glycol dimethacrylate (Shin Nakamura Chemical ■, manufactured 9
G) 0.25g.
ポリエチレングリコール（純正化学■製ＰＥＧ＃２００
）０．７５ｇ、過塩素酸リチウム０．０８ｇ、およびベ
ンゾイルパーオキサイド０．Ｏｌｇを混合し、均一溶液
とした。Polyethylene glycol (PEG #200 manufactured by Gensei Kagaku ■)
) 0.75 g, lithium perchlorate 0.08 g, and benzoyl peroxide 0. Olg was mixed to form a homogeneous solution.
この均一溶液とした液状組成物をアルミシャーレに薄く
流延し、これを、窒素雰囲気下７０℃で１４時間加熱硬
化して、厚さ３００ ＩＬｍのイオン伝導性高分子電解
質の硬化フィルムを得た。This homogeneous solution of the liquid composition was thinly cast into an aluminum petri dish, and heated and cured at 70°C for 14 hours in a nitrogen atmosphere to obtain a cured film of ion conductive polymer electrolyte with a thickness of 300 ILm. .
このフィルムに、２０ｗｔ％のピロールモノマーを直接
滴下し吸収させた。この七ツマー含浸イオン伝導性高分
子電解質フィルムの両側を、ＩＴＯガラスを電極として
挟み、定電流電解（電流密度５０ＩＬＡ／ｃｍ″）によ
り、３０分間、室温で重合させた０重合後、電極をはが
すと、ポリピロールとイオン伝導性高分子電解質の複合
膜が得られた。20 wt % of pyrrole monomer was directly dropped onto this film and absorbed. ITO glass was sandwiched between both sides of the 7-mer-impregnated ion-conductive polymer electrolyte film as electrodes, and polymerization was performed at room temperature for 30 minutes by constant current electrolysis (current density 50 ILA/cm''). After polymerization, the electrodes were peeled off. A composite membrane of polypyrrole and ion-conducting polymer electrolyte was obtained.
これに、負極活物質としてリチウム箔、外装板兼集電体
としてステンレス箔をｖＬ層し、電池を形成した。This was covered with a VL layer of lithium foil as a negative electrode active material and stainless steel foil as an exterior plate and current collector to form a battery.
得られた電池について、２０ｐＡ／ｃｍ’の定電流を２
０分間通電した後、２０ｐＡ／ｃｒｎ’の一定電流で、
放電電圧がＩＶに達するまでを１サイクルとする充放電
試験を行ない、その寿命性箋を調べた０本発明の電池は
、クーロン効率１００％で３００回以上の充放電を繰り
返すことができた。For the obtained battery, a constant current of 20 pA/cm' was applied to 2
After applying current for 0 minutes, at a constant current of 20 pA/crn',
A charging/discharging test was conducted in which one cycle was defined as the time until the discharge voltage reached IV, and the life characteristics of the battery were examined.The battery of the present invention was able to be repeatedly charged and discharged more than 300 times with a coulombic efficiency of 100%.
Claims (1)
、その両側に電極をはさみ、電解重合によりイオン伝導
性高分子電解質の表面に電子伝導性高分子を形成させて
得られた、電子伝導性高分子とイオン伝導性高分子電解
質の複合フィルムのうち、電子伝導性高分子を正極、お
よびイオン伝導性高分子電解質を電解質隔膜として用い
ることを特徴とする電池の製造法。An electronically conductive polymer obtained by impregnating a raw material monomer into an ionically conductive polymer electrolyte, sandwiching electrodes on both sides, and forming an electronically conductive polymer on the surface of the ionically conductive polymer electrolyte through electrolytic polymerization. A method for manufacturing a battery, comprising using an electron-conductive polymer as a positive electrode and an ion-conductive polymer electrolyte as an electrolyte diaphragm in a composite film of molecules and an ion-conductive polymer electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62012272A JPS63181273A (en) | 1987-01-23 | 1987-01-23 | Manufacture of cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62012272A JPS63181273A (en) | 1987-01-23 | 1987-01-23 | Manufacture of cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63181273A true JPS63181273A (en) | 1988-07-26 |
Family
ID=11800729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62012272A Pending JPS63181273A (en) | 1987-01-23 | 1987-01-23 | Manufacture of cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63181273A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63257634A (en) * | 1987-04-15 | 1988-10-25 | 株式会社リコー | Continuous manufacture of laminated and/or composite body film |
| JPH0240867A (en) * | 1988-07-29 | 1990-02-09 | Nippon Oil Co Ltd | Entirely solid secondary battery |
| KR100424256B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Process for preparing an polymer electolyte by electrochemical polymerization and lithium battery employing such process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62296376A (en) * | 1986-06-16 | 1987-12-23 | Yuasa Battery Co Ltd | Manufacture of polymer solid electrolyte battery |
-
1987
- 1987-01-23 JP JP62012272A patent/JPS63181273A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62296376A (en) * | 1986-06-16 | 1987-12-23 | Yuasa Battery Co Ltd | Manufacture of polymer solid electrolyte battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63257634A (en) * | 1987-04-15 | 1988-10-25 | 株式会社リコー | Continuous manufacture of laminated and/or composite body film |
| JPH0240867A (en) * | 1988-07-29 | 1990-02-09 | Nippon Oil Co Ltd | Entirely solid secondary battery |
| KR100424256B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Process for preparing an polymer electolyte by electrochemical polymerization and lithium battery employing such process |
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