JPH01122573A - Solid electrolyte cell - Google Patents
Solid electrolyte cellInfo
- Publication number
- JPH01122573A JPH01122573A JP62281219A JP28121987A JPH01122573A JP H01122573 A JPH01122573 A JP H01122573A JP 62281219 A JP62281219 A JP 62281219A JP 28121987 A JP28121987 A JP 28121987A JP H01122573 A JPH01122573 A JP H01122573A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- battery
- cell
- sheet
- electrolyte
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 41
- 229920000620 organic polymer Polymers 0.000 claims abstract description 11
- 229920000767 polyaniline Polymers 0.000 claims abstract description 3
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000005486 organic electrolyte Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910003092 TiS2 Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 229910011312 Li3VO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002781 RbAg4I5 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は固体電解質電池に関するもので、さらに詳しく
は、有機高分子電極と固体電解質からなる電池に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a solid electrolyte battery, and more particularly to a battery comprising an organic polymer electrode and a solid electrolyte.
従来の技術
固体電解質を使用した電気化学セル、特に固体電解質電
池の開発が最近盛んになって来ている。BACKGROUND OF THE INVENTION The development of electrochemical cells using solid electrolytes, particularly solid electrolyte batteries, has recently become active.
なかでもイオン伝導性固体電解質として、例えば、ｘ−
Ｌｉ４ＧｅＯａ −（１ｘ）Ｌｉｓ Ｏａを使用し、負
極としてリチウム金属を、正極おしてＴｉＳ２を使用し
た固体リチウム二次電池あるいはＲｂＣｕ４ｌ２−ｘＣ
１３＋８を固体電解質として使用し、負極として銅金属
を、正極としてＴｉＳ２を使用した固体二次電池の開発
が盛んである。こうした固体二次電池の作成に関しては
、太き（分けて二つの方法が知られている。即ち、蒸着
またはスパッタ等の薄膜製造装置を使用して作成する方
法とプレス機械により加圧成型して作成する方法がある
。Among them, as an ion conductive solid electrolyte, for example, x-
Solid lithium secondary battery using Li4GeOa - (1x)Lis Oa, lithium metal as the negative electrode and TiS2 as the positive electrode or RbCu4l2-xC
Solid secondary batteries using 13+8 as a solid electrolyte, copper metal as a negative electrode, and TiS2 as a positive electrode are being actively developed. There are two known methods for producing such solid-state secondary batteries: one using thin film production equipment such as vapor deposition or sputtering, and the other using pressure molding using a press machine. There is a way to create one.
−例として、固体リチウム二次電池の製造方法について
述べる。該電池に使用する固体電解質の作成に際しては
、高純度のＬｉ２ＣＯ３とＳｉＯ２さらにｖ２０５粉末
を所定の含有量となるよう秤量し、有機溶媒中（例えば
、ｎ−へキサンを使用する。）に分散し、これらを充分
に混合する。然る後、有機溶媒を分離乾燥した後、６０
０℃で加熱し、ＣＯ２が発生しなくなるまで、これらを
熱分解さぜる（通常、約１時間焼成加熱すると炭酸ガス
の発生は止まる）。- As an example, a method for manufacturing a solid-state lithium secondary battery will be described. When creating the solid electrolyte used in the battery, high-purity Li2CO3, SiO2, and V205 powder are weighed to a predetermined content and dispersed in an organic solvent (for example, using n-hexane). , mix these thoroughly. After that, after separating and drying the organic solvent, 60
These are heated at 0° C. and thermally decomposed until CO2 is no longer generated (usually, the generation of carbon dioxide gas stops after firing and heating for about 1 hour).
その後、７００℃で約４０時間焼成すると固溶体が得ら
れる。これを冷却した後、粉砕し、粒径が数μｍの微粉
末とする。さらに、該微粉末を金型を用い、数）ッ／
ｃｎ？の圧力で所望の大きさ、厚さに加圧成型し、さら
に、１０００℃で約１時間焼成し固体電解質として使用
する。Thereafter, a solid solution is obtained by firing at 700° C. for about 40 hours. After cooling this, it is pulverized to form a fine powder with a particle size of several μm. Furthermore, using a mold, the fine powder is
cn? It is pressure-molded to a desired size and thickness at a pressure of 1,000° C., and then fired at 1,000° C. for about 1 hour to be used as a solid electrolyte.
こうして得た固体電解質の一方の面に正極活物質として
ＴｉＳ２と固体電解質との混合物を加圧成型して得た成
型体を、他方の面に負極活物質としてリチウム金属をそ
れぞれ圧着して電池素子が構成される。また、これら固
体電解質電池の作成は、乾燥気体雰囲気中で行う必要が
ある。以」二の様に固体電解質電池の作成は、極めて作
業能率が悪く生産性に欠けるものであった。A molded body obtained by pressure molding a mixture of TiS2 and solid electrolyte as a positive electrode active material on one side of the solid electrolyte obtained in this way, and lithium metal as a negative electrode active material on the other side to form a battery element. is configured. Furthermore, these solid electrolyte batteries need to be created in a dry gas atmosphere. As mentioned above, the production of solid electrolyte batteries was extremely inefficient and lacked productivity.
このような問題を解決するために、発明者らは固体電解
質および電極材料に弾性を有する結着材を混合した電解
質シートおよび電極シートさらに、これらを使用したシ
ート状電池について提案した。しかし、この電池におい
てはＴｉＳ２に可逆的に入るリチウムの量が制限され大
きな容量の電池を得ることが出来ないという問題を有し
ていた。In order to solve such problems, the inventors proposed an electrolyte sheet and an electrode sheet in which a solid electrolyte and an electrode material are mixed with an elastic binder, and also a sheet-shaped battery using these sheets. However, this battery has a problem in that the amount of lithium that reversibly enters TiS2 is limited, making it impossible to obtain a battery with a large capacity.
一方、有機高分子電解重合膜を電極とし、有機電解液を
用いた電池が、盛んに研究されている。On the other hand, batteries using an organic electrolyte polymer membrane as an electrode and an organic electrolyte are being actively researched.
発明が解決しようとする問題点
この電池は、電池容量が有機溶媒中に溶解した支持電解
質、例えばＬ ｉ Ｃ］ ＯａなどのＬｉイオン濃度に
より規制され、また、有機溶媒に溶解しうる支持電解質
の量が太き（ないため、大きい容量の電池を提供するこ
とが出来ないという問題を有していた。Problems to be Solved by the Invention In this battery, the battery capacity is regulated by the Li ion concentration of a supporting electrolyte dissolved in an organic solvent, such as Li C]Oa, and the capacity of the battery is regulated by the concentration of Li ions such as Li The problem was that it was not possible to provide a battery with a large capacity because it had a large capacity.
本発明は、上記従来技術に鑑み、固体電解質電池をシー
ト状で形成し、電池容量の大きい可逆性に優れた電池を
提供することを目的とする。SUMMARY OF THE INVENTION In view of the above-mentioned prior art, an object of the present invention is to form a solid electrolyte battery in the form of a sheet and provide a battery with a large capacity and excellent reversibility.
問題点を解決するための手段
電極集電体にイオンが層間に可逆的に出入する有機高分
子膜を形成し、少なくとも正極、負極のいずれかとして
用い、予め用意した固体電解質シートに接触させ電池を
形成する。Means to Solve the Problem Form an organic polymer film on the electrode current collector through which ions reversibly move in and out between the layers, use it as at least either the positive electrode or the negative electrode, and contact it with a solid electrolyte sheet prepared in advance to form a battery. form.
作用 。Effect.
有機高分子膜を電極とし、有機電解液を用いた電池では
、電池容量が有機溶媒中に溶解した支持電解質の濃度、
により規制され大きな容量の電池を作ることが出来なか
ったが、シート状固体電解質を用いた電池では、該固体
電解質中のＬｉイオン濃度が４機電解液に比べ非常に大
きいため大きい容量の電池が可能となり、また、フレキ
シブルな電池が専易に作成することが出来る。In a battery using an organic polymer membrane as an electrode and an organic electrolyte, the battery capacity depends on the concentration of the supporting electrolyte dissolved in the organic solvent,
However, in batteries using a sheet-like solid electrolyte, the Li ion concentration in the solid electrolyte is much higher than that in a four-layer electrolyte, making it impossible to create a battery with a large capacity. In addition, flexible batteries can be easily produced.
実施例
本発明に使用される固体電解質シードとしては、銀イオ
ン、銅イオン、リチウムイオン、□゛プロトン、−価の
陽イオン伝導性無機固体電解質、あるいはフッ化物イオ
ン、塩化物イオン、臭化物イオン等、−価の陰イオン伝
導性無機固′体電解質の粉体と絶縁性高分子弾性体とか
らなり□、特に、ＲｂＣｕ４ｌ２−ｘＣ１３＋ｘ（Ｘ；
０．２〜０．６）、ＲｂＡｇ４Ｉ５．ｏ、４Ｌ ｉ４ｓ
ｉｏ、、−ｏ、６Ｌｉ３ｖＯ４等がイオン伝導性が優
れており本目的には好ましい固体電解質である。Examples The solid electrolyte seeds used in the present invention include silver ions, copper ions, lithium ions, □゛protons, -valent cation-conducting inorganic solid electrolytes, or fluoride ions, chloride ions, bromide ions, etc. , consisting of a -valent anion-conductive inorganic solid electrolyte powder and an insulating polymeric elastomer □, in particular, RbCu4l2-xC13+x (X;
0.2-0.6), RbAg4I5. o, 4L i4s
io, -o, 6Li3vO4, etc. have excellent ionic conductivity and are preferred solid electrolytes for this purpose.
また、絶縁性高分子弾、性体としては、例えば１．４−
ポリブタジェン、天然ゴム、ポリイソプレン、ＳＢＲ，
ＮＢ、Ｒ，、、ＥＰ’ＤＭ、、ＥＰ、Ｍ、ウレタンゴム
、ポリエステル系ゴム、クロロプレンゴム、エピクロル
ヒドリンゴム、シリコーンゴム、スチレン−ブタジェン
−スチレンブロック共重合体（ＳＢＳ） 、スチレン−
イソプレン−スチレンブロック共重合体（Ｓｌ、Ｓ）、
スチレンーエチレンーブ、チレンースチレン共重合体＜
５ＥＢＳ）、ブチルゴム、中スフアゼンゴム、ポリエチ
レン、ポリプロピレン、ポリエチレオキシド、ポリプロ
ピレンオキシド、ポリスチレン、塩化ビニール、エチレ
ン−酢酸エチル共重合体、１．２−ポ、リプタジエン、
エポキシ樹脂、フェノール樹脂、環化ポリブタジエ、ン
、環化ポリイソプレン、ポリメタクリル酸メチル、フッ
素樹脂およびこれらの混合物が挙げられるが、電極との
接着性および電気化学的安定性の点からＳＢＳ、Ｓ Ｉ
ｓ、５ＥＢＳ。In addition, as an insulating polymer elastic, for example, 1.4-
Polybutadiene, natural rubber, polyisoprene, SBR,
NB, R,, EP'DM, EP, M, Urethane rubber, Polyester rubber, Chloroprene rubber, Epichlorohydrin rubber, Silicone rubber, Styrene-butadiene-styrene block copolymer (SBS), Styrene-
Isoprene-styrene block copolymer (Sl, S),
Styrene-ethyleneb, styrene-styrene copolymer<
5EBS), butyl rubber, medium sulfur rubber, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polystyrene, vinyl chloride, ethylene-ethyl acetate copolymer, 1.2-po, liptadiene,
Examples include epoxy resin, phenol resin, cyclized polybutadiene, cyclized polyisoprene, polymethyl methacrylate, fluororesin, and mixtures thereof, but from the viewpoint of adhesion with electrodes and electrochemical stability, SBS, S I
s, 5EBS.
１．２−ポリブタジェン、シリコーンゴム、フッ素樹脂
等の可塑性を有するものが好ましい。1.2-Plastic materials such as polybutadiene, silicone rubber, and fluororesin are preferred.
固体電解質粉体を絶縁性高分子弾性体中に均一に分散さ
せ、シート化する方法としては、銀イオンまたは銅イオ
ン伝導性の固体電解質粉末を体積分率で５５〜９５％に
なるように芳香族炭化水素溶剤、ハロゲン化炭化水素溶
剤およびエステル系溶剤から選ばれる少なくとも１種の
溶剤に絶縁性高分子弾性体を体積分率で５〜４５％溶解
した溶液に混合し、得られた混合溶液を基盤上に塗布し
乾燥することによ、す、硬度が６５〜９６ （ＡＳＴＭ
Ａ硬度）で厚さが１０〜２５０μｍのシートを作ること
が出来る。A method for uniformly dispersing solid electrolyte powder in an insulating polymer elastomer and forming a sheet is to add aromatic solid electrolyte powder that conducts silver ions or copper ions to a volume fraction of 55 to 95%. A mixed solution obtained by mixing a solution in which an insulating polymeric elastomer is dissolved at a volume fraction of 5 to 45% in at least one solvent selected from group hydrocarbon solvents, halogenated hydrocarbon solvents, and ester solvents. By applying it on the base and drying it, the hardness is 65-96 (ASTM
A sheet with a thickness of 10 to 250 μm can be made.
一方、電池用電極としてステンレススチール薄膜上に電
解重合用電解液中で陽極酸化し、電解重合膜を形成し正
極または負極として用いた。この電極間に前記固体電解
質シートを介在させ電池を構成した。On the other hand, as an electrode for a battery, a stainless steel thin film was anodized in an electrolytic solution for electrolytic polymerization to form an electrolytic polymer film, which was used as a positive electrode or a negative electrode. A battery was constructed by interposing the solid electrolyte sheet between the electrodes.
以下、本発明を実施例を用い説明するが、本発明は、こ
れら実施例に限定されるものではない。Hereinafter, the present invention will be explained using Examples, but the present invention is not limited to these Examples.
（実施例１）
固体電解質として、０．４ Ｌ ｉＳ ｉ０２ ０．６
Ｌｉ３ＶＯ４を用い、該固体電解質の粉末（粒径、２μ
ｍ以下）を体積分率で９０％となるようにスチレン−ブ
タジェン−スチレンブロック共重合体く日本合成ゴム社
製ＴＲ−２０００）をトルエン中に溶解させた溶液（ス
チレン−ブタジェン−スチレンブロック共重合体の体積
分率は１０％）とボールミルにて充分混練し、該固体電
解質粉末を分散させた溶液を作成した。得られた溶液を
速やかにスピナーにて、予めステンレススチール箔を集
電体として使用し作成したポリピロール電解重合膜電極
上に塗布し、これら２枚の電極電解質膜（１枚；Ｉｃｍ
、１ｃｍ、厚さ０．５ｍｍ）を対向し、電解質同志接触
させた後、弾性を有するエポキシ樹脂でシールし、電池
を作成した。(Example 1) As a solid electrolyte, 0.4 L iS i02 0.6
Using Li3VO4, the solid electrolyte powder (particle size, 2μ
A solution of styrene-butadiene-styrene block copolymer (TR-2000 manufactured by Nippon Gosei Rubber Co., Ltd.) dissolved in toluene (styrene-butadiene-styrene block copolymer The volume fraction of the combined solid electrolyte powder was 10%) and was sufficiently kneaded in a ball mill to prepare a solution in which the solid electrolyte powder was dispersed. The obtained solution was quickly applied with a spinner onto a polypyrrole electrolyte polymer membrane electrode prepared in advance using stainless steel foil as a current collector, and these two electrode electrolyte membranes (1 sheet; Icm
, 1 cm, thickness 0.5 mm) were placed facing each other and brought into contact with the electrolyte, and then sealed with an elastic epoxy resin to prepare a battery.
得られた電池を５００μＡ ／ ｃｒＫで充放電した結
果、約１．２ｍＡｈｒの容量を示す電池が得られた。As a result of charging and discharging the obtained battery at 500 μA/crK, a battery exhibiting a capacity of about 1.2 mAh was obtained.
比較のために前記電極を同様の条件のもとで作成し、０
、３ Ｍ Ｌ ｉＣＩ ０４／プロピレンカーボネ
ート電解液を用い電池を作成し、同様の充放電を行った
結果、約０．２ｍＡｈｒの容量しか示さないことが判明
した。For comparison, the electrode was made under similar conditions and
, 3M LiCI 04/propylene carbonate electrolyte, and as a result of similar charging and discharging, it was found that the battery had a capacity of only about 0.2 mAh.
（実施例２）
実施例１と同様の固体電解質０．４Ｌｉ４Ｓｉ０２ ０
．６Ｌｉ３ＶＯ４粉末（粒径、２μｍ以下）を体積分率
で９０％になるようにスチレン−エチレン−ブチレン−
スチレン共重合体（ＳＥＢＳ；日本合成ゴム社製ＫＲＡ
ＴＯＮ Ｇ１６５０）をトルエン中に溶解させた溶液
（ＳＥＢＳ共重合体の体積分率は１０％）とボールミル
にて充分混練し、該固体電解質を分散させた溶液を作成
した。得られた溶液を速やかにスピナーにて、予めステ
ンレススチール箔を集電体として使用し作成したポリア
ニリン電解重合膜電極上に塗布し、これら２枚の電極電
解質膜（１枚；１ｃｍ、１ｃｍ、厚さ０．５ｍｍ）を対
向し、電解質同志接触させた後、弾性を有するエポキシ
樹脂でシールし、電池を作成した。(Example 2) Solid electrolyte 0.4Li4Si02 0 similar to Example 1
．． 6Li3VO4 powder (particle size, 2 μm or less) was mixed with styrene-ethylene-butylene at a volume fraction of 90%.
Styrene copolymer (SEBS; KRA manufactured by Japan Synthetic Rubber Co., Ltd.
TON G1650) dissolved in toluene (the volume fraction of the SEBS copolymer was 10%) was sufficiently kneaded in a ball mill to create a solution in which the solid electrolyte was dispersed. The obtained solution was quickly applied with a spinner onto a polyaniline electrolyte polymer membrane electrode prepared in advance using stainless steel foil as a current collector, and these two electrode electrolyte membranes (1 sheet; 1 cm, 1 cm thick, After the electrolytes were brought into contact with each other (with a diameter of 0.5 mm), they were sealed with an elastic epoxy resin to prepare a battery.
得られた電池を５００μＡ ／ ｃｕｔで充放電した結
果、約１．５ｍＡｈｒの容量を示す電池が得られた。As a result of charging and discharging the obtained battery at 500 μA/cut, a battery exhibiting a capacity of about 1.5 mAh was obtained.
比較のために前記電極を同様の条件のもとで作成し、０
、３ Ｍ Ｌ ｉＣＩ Ｏ４／プロピレンカーボネ
ート電解液を用い電池を作成し、同様の充放電を行った
結果、約０．３ｍＡｈｒの容量しか示さないことが判明
した。For comparison, the electrode was made under similar conditions and
, 3 M LiCI O4/propylene carbonate electrolyte solution was used to prepare a battery, and as a result of similar charging and discharging, it was found that the battery had a capacity of only about 0.3 mAh.
（実施例３）
実施例１と同様の固体電解質０．４Ｌｉ４Ｓｉ０２−０
．６Ｌ １３ＶＯ４粉末（粒径、２ｔｔｍ以下）を体積
分率で９０％になるようにスチレン−エチレン−ブチレ
ン−スチレン共重合体（ＳＥＢＳ ；日本合成ゴム社製
ＫＲＡＴＯＮ Ｇ１６５０）をトルエン中に溶解させ
た溶液（ＳＥＢＳ共重合体の体積分率は１０％）とボー
ルミルにて充分混練し、該固体電解質を分散させた溶液
を作成した。(Example 3) Solid electrolyte 0.4Li4Si02-0 similar to Example 1
．． A solution in which styrene-ethylene-butylene-styrene copolymer (SEBS; KRATON G1650 manufactured by Nihon Gosei Rubber Co., Ltd.) was dissolved in toluene so that the volume fraction of 6L 13VO4 powder (particle size, 2ttm or less) was 90%. (The volume fraction of the SEBS copolymer was 10%) was sufficiently kneaded in a ball mill to prepare a solution in which the solid electrolyte was dispersed.
得られた溶液を速やかにスピナーにて、予めステンレス
スチール箔を集電体として使用し作成したポリチェニレ
ン電解重合膜電極上に塗布し、これら２枚の電極電解質
膜（１枚ｉ １ Ｃｍ ＋ Ｉ Ｃｍ １厚さ０．５＋
ｎｍ）を対向し、電解質同志接触させた後、弾性を有す
るエポキシ樹脂でシールし、電池を作成した。The obtained solution was immediately applied with a spinner onto a polythenylene electrolyte polymer membrane electrode prepared in advance using stainless steel foil as a current collector, and these two electrode electrolyte membranes (1 sheet i 1 Cm + I Cm 1 thickness 0.5+
After facing the electrolytes and bringing them into contact with each other, the batteries were sealed with an elastic epoxy resin to prepare a battery.
得られた電池を５００μＡ ／ ｃｎｆで充放電した結
果、約１．４ｍＡｈｒの容量を示す電池が得られた。As a result of charging and discharging the obtained battery at 500 μA/cnf, a battery exhibiting a capacity of about 1.4 mAh was obtained.
比較のために前記電極を同様の条件のもとで作成し、０
．３Ｍ ＬｉＣｌ０ａ／プロピレンカーボネート電解
液を用い電池を作成し、同様の充放電を行った結果、約
０．２ｍＡｈｒの容量しか示さないことが判明゛した。For comparison, the electrode was made under similar conditions and
．． When a battery was prepared using a 3M LiCl0a/propylene carbonate electrolyte and similarly charged and discharged, it was found that the battery had a capacity of only about 0.2 mAh.
発明の効果
以上のように、本発明の固体電解質電池は、有機高分子
膜を電極とし、有機電解液を用いた電池に比べ電池容量
が大きく、また、フレキシブルな大面積のシート電池を
容易に作成することができるものである。Effects of the Invention As described above, the solid electrolyte battery of the present invention uses an organic polymer membrane as an electrode, has a larger battery capacity than a battery using an organic electrolyte, and can be easily fabricated into a flexible, large-area sheet battery. It is something that can be created.
Claims (3)
機高分子を主体としてなる電極を設置したことを特徴と
する固体電解質電池。(1) A solid electrolyte battery characterized in that an electrode mainly composed of an organic polymer is provided on at least one surface of a sheet-like solid electrolyte.
合により形成した有機重合膜を使用したことを特徴とす
る特許請求の範囲第１項記載の固体電解質電池。(2) The solid electrolyte battery according to claim 1, wherein an organic polymer film formed by electrolytic polymerization is used as an electrode mainly composed of an organic polymer.
ン、ポリピロール、ポリチェニレンから選ばれる少なく
とも１種以上の電解重合膜を使用したことを特徴とする
特許請求の範囲第１項または第２項記載の固体電解質電
池。(3) The solid according to claim 1 or 2, wherein the organic polymer film formed by electrolytic polymerization uses at least one electrolytic polymer film selected from polyaniline, polypyrrole, and polythenylene. electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62281219A JPH01122573A (en) | 1987-11-06 | 1987-11-06 | Solid electrolyte cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62281219A JPH01122573A (en) | 1987-11-06 | 1987-11-06 | Solid electrolyte cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01122573A true JPH01122573A (en) | 1989-05-15 |
Family
ID=17636025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62281219A Pending JPH01122573A (en) | 1987-11-06 | 1987-11-06 | Solid electrolyte cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01122573A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03269012A (en) * | 1990-03-19 | 1991-11-29 | Fuji Photo Film Co Ltd | New electronic conductive polymer and electrically conductive material using same polymer |
| JP2018107095A (en) * | 2016-12-27 | 2018-07-05 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Solid electrolyte, and lithium battery prepared therewith |
-
1987
- 1987-11-06 JP JP62281219A patent/JPH01122573A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03269012A (en) * | 1990-03-19 | 1991-11-29 | Fuji Photo Film Co Ltd | New electronic conductive polymer and electrically conductive material using same polymer |
| JP2018107095A (en) * | 2016-12-27 | 2018-07-05 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Solid electrolyte, and lithium battery prepared therewith |
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