JPH04248257A - Solid electrode composition - Google Patents
Solid electrode compositionInfo
- Publication number
- JPH04248257A JPH04248257A JP3007501A JP750191A JPH04248257A JP H04248257 A JPH04248257 A JP H04248257A JP 3007501 A JP3007501 A JP 3007501A JP 750191 A JP750191 A JP 750191A JP H04248257 A JPH04248257 A JP H04248257A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ion
- powder
- solid
- aluminum
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 150000001450 anions Chemical group 0.000 claims abstract description 3
- 230000005684 electric field Effects 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 10
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 125000002091 cationic group Chemical group 0.000 abstract 2
- 230000036647 reaction Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910009294 Li2S-B2S3 Inorganic materials 0.000 description 1
- 229910009346 Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002892 organic cations Chemical group 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、電池、キャパシター、
センサー、表示素子、記録素子等の電気化学素子に用い
られる固形電極組成物、とくに、リチウムイオン伝導性
の電解質と組み合わせて固体状のリチウム電池の負極と
して用いる固形電極組成物に関する。[Industrial Application Field] The present invention relates to batteries, capacitors,
The present invention relates to solid electrode compositions used in electrochemical devices such as sensors, display elements, and recording elements, and particularly to solid electrode compositions used in combination with lithium ion conductive electrolytes as negative electrodes of solid lithium batteries.
【０００２】0002
【従来の技術】固体の電解質を用いることで液漏れがな
く、小形薄形化の電池、電気二重層キャパシタ等の固体
の電気化学デバイスを得ることができる。2. Description of the Related Art By using a solid electrolyte, it is possible to obtain small and thin solid electrochemical devices such as batteries and electric double layer capacitors without liquid leakage.
【０００３】しかしながら、従来の固体電気化学的デバ
イスは、弾性に欠ける固体物質で素子が構成されること
から、機械的衝撃に対してはきわめて脆く、破損しやす
い欠点がある。この様な問題を解決するため、ポリエチ
レンオキシド（ＰＥＯ）とアルカリ金属塩とからなる高
分子固体電解質が提案されている（”Ｆａｓｔ Ｉｏｎ
Ｔｒａ−ｎｓｐｏｒｔ ｉｎ Ｓｏｌｉｄ” Ｐ
．Ｖａｎｉｓｈｓｔａｅｔ．ａｌ．， Ｅｄｓ． Ｐ．
１３１（１９７９） Ｎｏｒｔｈ Ｈｏｌａｎｄ Ｐ
ｕｂｌ−ｉｓｈｉｎｇ Ｃｏ．） 。高分子固体電解質
は無機系固体電解質に較べ、軽量で、柔軟性、成形性に
優れている。以来、優れた柔軟性、成形性を保持したま
まで無機系固体電解質に匹敵する高いイオン伝導性を示
す材料の研究開発が盛んに行われている。特に、金属リ
チウム負極と組み合わせることで電圧が３ボルト以上の
高エネルギー密度の固体二次電池が期待できることから
、盛んに研究開発が行われている。[0003] However, conventional solid-state electrochemical devices have the disadvantage that they are extremely brittle and easily damaged by mechanical impacts because their elements are constructed of solid materials lacking elasticity. In order to solve these problems, a solid polymer electrolyte consisting of polyethylene oxide (PEO) and an alkali metal salt has been proposed ("Fast Ion").
Transport in Solid”P
．． Vanishstate. al. , Eds. P.
131 (1979) North Holland P.
ubl-ishing Co. ). Polymer solid electrolytes are lighter and have superior flexibility and moldability compared to inorganic solid electrolytes. Since then, research and development has been actively conducted on materials that exhibit high ionic conductivity comparable to inorganic solid electrolytes while maintaining excellent flexibility and moldability. In particular, active research and development is being carried out on solid-state secondary batteries with high energy density and a voltage of 3 volts or more, which can be expected by combining it with a metallic lithium negative electrode.
【０００４】0004
【発明が解決しようとする課題】しかし、これまで提案
されている金属リチウムあるいはリチウムーアルミニウ
ムなどのリチウム合金を負極とするリチウム二次電池で
は、負極と高分子電解質との間で低分極性の可逆性の良
い均一な接合界面が必ずしも得られず、例えば、０．１
ｍＡ／ｃｍ２を越える電流密度の充放電では５０サイク
ル以下の充放電サイクルの初期においても分極が急激に
増大する問題があった。また、電解質層を破って金属リ
チウムが析出し短絡にいたるという問題があった。[Problems to be Solved by the Invention] However, in the lithium secondary batteries that have been proposed so far that use metallic lithium or lithium alloys such as lithium-aluminum as the negative electrode, there is a problem of low polarization between the negative electrode and the polymer electrolyte. A uniform bonding interface with good reversibility cannot always be obtained, for example, 0.1
When charging and discharging at a current density exceeding mA/cm2, there is a problem in that polarization increases rapidly even at the beginning of 50 or less charge/discharge cycles. Further, there was a problem that the electrolyte layer was broken and metallic lithium was deposited, leading to a short circuit.
【０００５】本発明はこのような課題を解決するもので
、固体状のリチウム二次電池用の負極として、イオン伝
導性と電子伝導性がともに優れた固形の電極組成物を得
ることを目的とするものである。[0005] The present invention is intended to solve these problems, and its purpose is to obtain a solid electrode composition having excellent ionic conductivity and electronic conductivity as a negative electrode for a solid lithium secondary battery. It is something to do.
【０００６】[0006]
【課題を解決するための手段】この課題を解決するため
に本発明は炭素粉末と、金属アルミニウムあるいはその
合金粉末と、エチレンオキサイド鎖（ＥＯ）またはプロ
ピレンオキサイド鎖（ＰＯ）のいずれかを有するカチオ
ン界面活性剤、あるいはエチレンオキサイド鎖（ＥＯ）
およびプロピレンオキサイド鎖を有するカチオン界面活
性剤と、イオン交換性の層状化合物と、式ＭＸで表され
るイオン性物質（ただし、Ｍは電界の作用で固形電極組
成物内を移動する金属イオン、プロトン、アンモニウム
イオンであり、Ｘは強酸のアニオンである）を少なくと
も含有させたものである。さらに電極組成物内のイオン
伝導性を大きくする目的でイオン伝導性の粒子を含有さ
せたものである。[Means for Solving the Problem] In order to solve this problem, the present invention provides carbon powder, metal aluminum or its alloy powder, and a cation having either an ethylene oxide chain (EO) or a propylene oxide chain (PO). Surfactant or ethylene oxide chain (EO)
and a cationic surfactant having a propylene oxide chain, an ion-exchange layered compound, and an ionic substance represented by the formula MX (where M is a metal ion or proton that moves within the solid electrode composition under the action of an electric field. , ammonium ion, and X is an anion of a strong acid). Furthermore, ion conductive particles are included for the purpose of increasing the ion conductivity within the electrode composition.
【０００７】[0007]
【作用】このようにして得られる固形電極組成物内にあ
っては、イオン性の化合物ＭＸはカチオン界面活性剤と
イオン交換性の層状化合物とで複合体を形成し層状化合
物の結晶の層間あるいは表面に高濃度に保持されイオン
伝導に有利な経路を形成する。また、炭素粉末および金
属アルミニウムあるいはアルミニウム合金粉末は、カチ
オン界面活性剤の作用により溶媒とイオン交換性の層状
化合物とが均一に混和される。さらに、イオン伝導性粉
末の添加混合に際しては、カチオン界面活性剤は金属粉
末の凝集を防止し、溶媒とイオン交換性の層状化合物、
炭素粉末、金属アルミニウム粉末あるいはその合金粉末
との均一な混合分散を可能にする。このようにして、高
い電子・イオン伝導性と均質性が発現される。その結果
、分極の小さい電極組成物となる。すなわち、電池反応
の進行に伴って、炭素粉末あるいは金属アルミニウムあ
るいはその合金粉末上へ負極金属が析出・溶解を繰り返
すが、本発明の電極組成物は均質で電極面積が大きいの
で電流の局部集中が起こり難い。さらに、負極金属の析
出はイオン交換性の層状化合物が介在することにより一
方向に起こり難くなり、電解質層を突き破って負極金属
が析出し、両極が短絡することはない。また、カチオン
界面活性剤のポリエチレンオキサイド鎖および／または
プロピレンオキサイド鎖とイオン交換性の層状化合物と
のマイクロポーラス構造とが絡まって良好な成形性と十
分な機械的強度が付与される。[Function] In the solid electrode composition thus obtained, the ionic compound MX forms a complex with the cationic surfactant and the ion-exchange layered compound, and forms a complex between the crystals of the layered compound. It is retained at a high concentration on the surface and forms an advantageous path for ion conduction. In addition, the carbon powder and the metallic aluminum or aluminum alloy powder are uniformly mixed with the solvent and the ion-exchangeable layered compound by the action of the cationic surfactant. Furthermore, when adding and mixing the ion conductive powder, the cationic surfactant prevents the agglomeration of the metal powder, and the solvent and the ion exchange layered compound,
Enables uniform mixing and dispersion of carbon powder, metal aluminum powder, or their alloy powder. In this way, high electronic and ionic conductivity and homogeneity are achieved. As a result, an electrode composition with low polarization is obtained. That is, as the battery reaction progresses, the negative electrode metal repeatedly precipitates and dissolves on carbon powder, metallic aluminum, or its alloy powder, but the electrode composition of the present invention is homogeneous and has a large electrode area, so that local concentration of current is prevented. Hard to happen. Furthermore, the presence of the ion-exchange layered compound makes it difficult for the negative electrode metal to precipitate in one direction, so that the negative electrode metal does not break through the electrolyte layer and precipitate, thereby preventing short-circuiting between the two electrodes. In addition, the microporous structure of the polyethylene oxide chain and/or propylene oxide chain of the cationic surfactant and the ion-exchangeable layered compound are entangled to provide good moldability and sufficient mechanical strength.
【０００８】[0008]
【実施例】以下、本発明の一実施例を説明するが、本発
明は以下の実施例に限定されるものではない。また、以
下の実施例において部、％、比は特に断わらない限り重
量部、重量％、重量比を表わす。[Example] An example of the present invention will be described below, but the present invention is not limited to the following example. Further, in the following examples, parts, percentages, and ratios represent parts by weight, percentages by weight, and weight ratios unless otherwise specified.
【０００９】本実施例の炭素材料としては、天然黒鉛、
人造黒鉛、無定形炭素、繊維状、粉末状、石油ピッチ系
、石炭コークス系のいずれも用いることができる。粒子
あるいは繊維の大きさは、直径あるいは繊維径が０．０
１〜１０μｍ、繊維長が数μｍから数ｍｍ までが望ま
しい。
金属アルミニウムまたはその合金粉末としては、Ａｌ，
Ａｌ−Ｆｅ， Ａｌ−Ｓｉ， Ａｌ−Ｚｎ， Ａｌ−
Ｌｉ， Ａｌ−Ｚｎ−Ｓｉなどの超急冷により得られた
フレーク状のものを、空気あるいは窒素などの不活性ガ
ス中で機械的な粉砕により得られた球状あるいは無定形
の粉末が用いられる。粒子の大きさは、直径１〜１００
μｍが望ましい。炭素材料とアルミニウムまたはアルミ
ニウム合金粉末との混合割合は、アルミニウムまたはア
ルミニウム合金粉末１部に対し炭素材料粉末０．０１〜
５．０部、望ましくは０．０５〜０．５部である。炭素
材料が０．０１部以下であるとアルミニウムまたはアル
ミニウム合金粉末との均一分散が困難になり、炭素粉末
が凝集しアルミニウムあるいはアルミニウム合金粒子間
の電導性が不良になり、電極として有効に働かなくなる
。また５．０部以上になるとアルミニウムまたはアルミ
ニウム合金粉末粒子が炭素粒子で厚く覆われてしまい、
電解質との接触が断たれ、電極が不安定になったり分極
が大きくなったりする。The carbon materials used in this example include natural graphite,
Any of artificial graphite, amorphous carbon, fibrous, powdered, petroleum pitch-based, and coal-coke-based materials can be used. The size of particles or fibers is 0.0 in diameter or fiber diameter.
Preferably, the fiber length is 1 to 10 μm, and the fiber length is from several μm to several mm. Metal aluminum or its alloy powder includes Al,
Al-Fe, Al-Si, Al-Zn, Al-
Spherical or amorphous powder obtained by mechanically pulverizing flakes obtained by ultra-quenching Li, Al-Zn-Si, etc. in air or an inert gas such as nitrogen is used. The particle size is 1 to 100 mm in diameter.
μm is desirable. The mixing ratio of carbon material and aluminum or aluminum alloy powder is 0.01 to 1 part of carbon material powder to 1 part of aluminum or aluminum alloy powder.
The amount is 5.0 parts, preferably 0.05 to 0.5 parts. If the carbon material is less than 0.01 part, it will be difficult to uniformly disperse the aluminum or aluminum alloy powder, the carbon powder will aggregate, the conductivity between aluminum or aluminum alloy particles will be poor, and the material will not work effectively as an electrode. . Moreover, if the amount exceeds 5.0 parts, the aluminum or aluminum alloy powder particles will be thickly covered with carbon particles.
Contact with the electrolyte is broken, causing the electrode to become unstable and polarized.
【００１０】本発明のＥＯ鎖およびＰＯ鎖を有するカチ
オン界面活性剤、あるいはＥＯ鎖またはＰＯ鎖のいずれ
かを有するカチオン活性剤としては、例えば下式（化１
）あるいは（化２）で示されるものが挙げられる。[0010] The cationic surfactant having an EO chain and a PO chain, or a cationic surfactant having either an EO chain or a PO chain of the present invention is, for example, represented by the following formula (Chemical formula 1).
) or (Chemical formula 2).
【００１１】[0011]
【化１】[Chemical formula 1]
【００１２】式中、Ｙは窒素あるいは燐、Ａ−はＣｌ，
−Ｂｒ−，Ｉ−，Ｆ−，ＣｌＯ４−，ＣＨ３ＣＯＯ−，
ＣＦ３ＳＯ３−，ＯＨ−，ＣＨ３ＳＯ３−，ＡｌＣｌ４
−，ＢＦ４−，ＰＦ６−，ＮＯ２−またはこれらの組合
せ、Ｒ１，Ｒ２，Ｒ３，Ｒ４の少なくとも一つはＥＯ鎖
あるいは、およびＰＯ鎖を有する置換基を有するあるい
は有しない炭素数１から３０個の炭化水素基であり、残
りは水素あるいは置換基を有するあるいは有しない炭素
数１から３０個の同じあるいは異なる炭化水素基である
。 ＥＯ鎖あるいは、およびＰＯ鎖の付加モル数は２
０から５００が望ましい。In the formula, Y is nitrogen or phosphorus, A- is Cl,
-Br-, I-, F-, ClO4-, CH3COO-,
CF3SO3-, OH-, CH3SO3-, AlCl4
-, BF4-, PF6-, NO2- or a combination thereof; at least one of R1, R2, R3, R4 has 1 to 30 carbon atoms with or without a substituent having an EO chain or a PO chain; The rest are hydrogen or the same or different hydrocarbon groups having 1 to 30 carbon atoms with or without a substituent. The number of added moles of EO chain or PO chain is 2
0 to 500 is desirable.
【００１３】[0013]
【化２】[Case 2]
【００１４】式中、Ｚは硫黄、Ａ−はＣｌ，−Ｂｒ−，
Ｉ−，Ｆ−，ＣｌＯ４−，ＣＨ３ＣＯＯ−，ＣＦ３ＳＯ
３−，ＯＨ−，ＣＨ３ＳＯ３−，ＡｌＣｌ４−，ＢＦ４
−，ＰＦ６−，ＮＯ２−またはこれらの組合せ、Ｒ１，
Ｒ２，Ｒ３，Ｒ４の少なくとも一つはＥＯ鎖あるいは、
およびＰＯ鎖を有する置換基を有する、あるいは有しな
い炭素数１から３０個の炭化水素基であり、残りは水素
あるいは置換基を有する、あるいは有しない炭素数１か
ら３０個の同じあるいは異なる炭化水素基である。In the formula, Z is sulfur, A- is Cl, -Br-,
I-, F-, ClO4-, CH3COO-, CF3SO
3-, OH-, CH3SO3-, AlCl4-, BF4
-, PF6-, NO2- or a combination thereof, R1,
At least one of R2, R3, and R4 is an EO chain or
and a hydrocarbon group having 1 to 30 carbon atoms with or without a substituent having a PO chain, and the remainder being hydrogen or the same or different hydrocarbon group having 1 to 30 carbon atoms with or without a substituent. It is the basis.
【００１５】このカチオン界面活性剤の添加量は、固形
電極組成物全量に対し、０．５から２０％が望ましい。The amount of the cationic surfactant added is preferably 0.5 to 20% based on the total amount of the solid electrode composition.
【００１６】イオン性物質としては、特に制限はないが
、ＬｉＩ， ＬｉＣｌＯ４， ＬｉＣＦ３ＳＯ３， Ｌ
ｉＰＦ６， ＬｉＢＦ４， ＬｉＳＣＮ， ＬｉＡｓＦ
６などの可溶性のリチウム塩が用いられる。[0016] There are no particular restrictions on the ionic substance, but LiI, LiClO4, LiCF3SO3, L
iPF6, LiBF4, LiSCN, LiAsF
A soluble lithium salt such as 6 is used.
【００１７】イオン交換性の層状化合物としては、モン
モリロナイト、ヘクトライト、サポナイト、スメクタイ
トなどのけい酸塩を含む粘土鉱物、りん酸ジルコニウム
、りん酸チタニウムなどのりん酸エステル、バナジン酸
、アンチモン酸、タングステン酸、あるいは、それらを
第４級アンモニウム塩等の有機カチオンあるいはエチレ
ンオキサイド、プロピレンオキサイド等の有機の極性化
合物で変性したものが挙げられる。Examples of ion exchange layered compounds include clay minerals containing silicates such as montmorillonite, hectorite, saponite, and smectite, phosphate esters such as zirconium phosphate and titanium phosphate, vanadate, antimonic acid, and tungsten. Examples include acids, or those modified with organic cations such as quaternary ammonium salts, or organic polar compounds such as ethylene oxide and propylene oxide.
【００１８】さらにイオン伝導性の粉末としては、Ｌｉ
Ｉ、ＬｉＩ・Ｈ２Ｏ、Ｌｉ−β−Ａｌ２Ｏ３、ＬｉＩ−
Ｌｉ２Ｓ−Ｂ２Ｓ３、ＰＥＯ−ＬｉＣＦ３ＳＯ３などの
リチウムイオン伝導性固体電解質が望ましく用いられる
。イオン伝導性粉末の添加量は、固形電極組成物の成形
性が損なわれない限り制限はない。Furthermore, as the ion conductive powder, Li
I, LiI・H2O, Li-β-Al2O3, LiI-
Lithium ion conductive solid electrolytes such as Li2S-B2S3 and PEO-LiCF3SO3 are preferably used. There is no limit to the amount of ion conductive powder added as long as the moldability of the solid electrode composition is not impaired.
【００１９】本発明の固形電極組成物はつぎのようにし
て得られる。イオン性化合物を１〜５０％溶解した溶剤
にイオン交換性の層状化合物粉末を１〜５０％となるよ
うに加え、つぎにＥＯ鎖あるいは、およびＰＯ鎖を有す
るカチオン界面活性剤をスラリー全体に対して０．１〜
２０％の割合になるように加え、ディスパーサなどの混
合粉砕機により粉砕混合して固形分含量が５〜９５％の
電解質スラリーを調製する。The solid electrode composition of the present invention can be obtained as follows. Add 1 to 50% ion exchange layered compound powder to a solvent in which 1 to 50% of an ionic compound is dissolved, and then add a cationic surfactant having an EO chain or a PO chain to the entire slurry. Te 0.1~
The electrolyte slurry is added at a ratio of 20% and pulverized and mixed using a mixer such as a disperser to prepare an electrolyte slurry having a solid content of 5 to 95%.
【００２０】また、イオン性化合物を１から５０％溶解
した溶剤にＥＯ鎖あるいは、およびＰＯ鎖を有するカチ
オン界面活性剤を０．１〜２０％含むカチオン界面活性
剤溶液に、炭素粉末とアルミニウムあるいはアルミニウ
ム合金粉末とをあらかじめ混合した粉末を添加し電極ス
ラリーとする。つぎに、電解質スラリーと電極スラリー
を混合して電極組成物スラリーを得る。混合は、直径が
３〜１０ｍｍアルミナ球と一緒にアルミナボールミル中
で行うのが望ましい。このようにして得られた電極組成
物スラリーを、テフロン板やナイロンメッシュシートな
どの支持体上に流延あるいは塗布して成形した後、溶剤
を一部あるいは全部散逸させることで固形電解質組成物
を得ることができる。支持体がメッシュ状であれば支持
体を一体化したままで固形電極組成物として用いること
も可能である。必要に応じ、これらの工程は相対湿度が
４０％以下の乾燥雰囲気中で行われる。[0020] Also, carbon powder and aluminum or A pre-mixed powder with aluminum alloy powder is added to form an electrode slurry. Next, the electrolyte slurry and the electrode slurry are mixed to obtain an electrode composition slurry. Mixing is preferably carried out in an alumina ball mill with alumina balls having a diameter of 3 to 10 mm. The electrode composition slurry obtained in this manner is cast or coated onto a support such as a Teflon plate or a nylon mesh sheet and formed, and then the solid electrolyte composition is formed by dissipating some or all of the solvent. Obtainable. If the support is in the form of a mesh, it is possible to use it as a solid electrode composition with the support integrated. If necessary, these steps are performed in a dry atmosphere with a relative humidity of 40% or less.
【００２１】また、溶剤としては、アセトン、メチルエ
チルケトン、メチルイソブチルケトンなどのケトン系溶
剤、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、シク
ロヘキサンなどの飽和炭化水素系溶剤、ベンゼン、トル
エン、キシレンなどの芳香族系溶剤、酢酸エチル、酢酸
プチル、プロピレンカーボネートなどのエステル系溶剤
、メタノール、エタノール、イソプロピルアルコール、
エチレングリコール、グリセリン、ポリエチレングリコ
ールなどのアルコール系溶剤、アセトニトリルなどのニ
トリル類、あるいは水が用いられる。Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, saturated hydrocarbon solvents such as n-hexane, n-heptane, n-octane, and cyclohexane, and benzene, toluene, and xylene. Aromatic solvents, ester solvents such as ethyl acetate, butyl acetate, propylene carbonate, methanol, ethanol, isopropyl alcohol,
Alcohol solvents such as ethylene glycol, glycerin, and polyethylene glycol, nitriles such as acetonitrile, or water are used.
【００２２】（実施例１）（化３）で示されるカチオン
界面活性剤をアセトニトリルに溶解し２０％のカチオン
界面活性剤溶液を調整した。(Example 1) A cationic surfactant represented by (Chemical formula 3) was dissolved in acetonitrile to prepare a 20% cationic surfactant solution.
【００２３】[0023]
【化３】[Chemical formula 3]
【００２４】さらに、イオン性物質としてＬｉＣＦ３Ｓ
Ｏ３を１０％溶解したカチオン界面活性剤溶液に、固形
分含量が３０％となるように平均粒径が１５μｍのγー
りん酸ジルコニウム粉末を添加し、４０℃で２４時間撹
半混合し電解質スラリーを得た。つぎに、カチオン界面
活性剤溶液に平均粒径が１８μｍの純度９９．８％の金
属アルミニウム粉末１部と黒鉛化度４８％、平均粒径が
２μｍの人造黒鉛粉末０．１部との混合粉末を固形分含
量が５０％となるように加え４０℃で２４時間混合し電
極スラリーを得た。電解質スラリーと電極スラリーとを
固形分比が１：２となるようにアルミナボールミル中で
２４時間混合して電極組成物スラリーを得た。電極組成
物スラリーを平滑なテフロン製の板の上でドクターブレ
ードを用い塗布した後、１３０℃の乾燥アルゴン気流中
で１時間乾燥し、さらに５時間真空乾燥することにより
大きさ ８０ｘ８０ｍｍ、厚さ２１０μｍのシート状
の固形電極組成物を得た。また、電極組成物の電気化学
特性を評価する電解セルの構成用として、電解質スラリ
ーのみを同様にして塗布乾燥して大きさ８０ｘ８０ｍｍ
、厚さ９０ミクロンの電解質シートを作製した。Furthermore, LiCF3S is used as an ionic substance.
γ-zirconium phosphate powder with an average particle size of 15 μm was added to a cationic surfactant solution containing 10% O3 dissolved therein so that the solid content was 30%, and the mixture was stirred and mixed at 40°C for 24 hours to form an electrolyte slurry. I got it. Next, a mixed powder of 1 part of 99.8% pure metal aluminum powder with an average particle size of 18 μm and 0.1 part of artificial graphite powder with a degree of graphitization of 48% and an average particle size of 2 μm is added to the cationic surfactant solution. was added so that the solid content was 50% and mixed at 40°C for 24 hours to obtain an electrode slurry. Electrolyte slurry and electrode slurry were mixed in an alumina ball mill for 24 hours so that the solid content ratio was 1:2 to obtain an electrode composition slurry. After applying the electrode composition slurry on a smooth Teflon plate using a doctor blade, it was dried in a dry argon stream at 130°C for 1 hour, and then vacuum dried for 5 hours, resulting in a size of 80 x 80 mm and a thickness of 210 μm. A sheet-like solid electrode composition was obtained. In addition, for the construction of an electrolytic cell for evaluating the electrochemical properties of the electrode composition, only the electrolyte slurry was coated and dried in the same manner, and the size was 80 x 80 mm.
, an electrolyte sheet with a thickness of 90 microns was prepared.
【００２５】（実施例２）窒素ガス雰囲気中で粉砕した
球状の平均粒径が４０μｍのＡｌ−Ｓｉ合金（Ｓｉ含量
：２５原子％）粉末１部と、平均粒径７μｍ、純度９９
．９９％の高純度天然黒鉛０．１部とをエタノールを分
散媒として混合し、乾燥したものを電極粉末として用い
、（化４）で示されるカチオン性界面活性剤をアセトニ
トリルに溶解した１０％のカチオン界面活性剤溶液と、
平均粒径が２５μｍのモンモリロナイト粉末、イオン性
物質としてトリフルオロスルフォン酸リチウム（ＬｉＣ
Ｆ３ＳＯ３）とを用いた以外は実施例１と同様にして、
厚さが３００μｍのシート状電極組成物と厚さが１１０
μｍのシート状電解質を作製した。(Example 2) One part of spherical Al-Si alloy (Si content: 25 atomic %) powder with an average particle size of 40 μm crushed in a nitrogen gas atmosphere, and an average particle size of 7 μm with a purity of 99
．． 0.1 part of 99% high-purity natural graphite was mixed with ethanol as a dispersion medium, and the dried product was used as an electrode powder. a cationic surfactant solution;
Montmorillonite powder with an average particle size of 25 μm, lithium trifluorosulfonate (LiC) as an ionic substance
F3SO3) was used in the same manner as in Example 1,
Sheet electrode composition with a thickness of 300 μm and a thickness of 110 μm
A sheet-like electrolyte of μm size was produced.
【００２６】[0026]
【化４】[C4]
【００２７】実施例３
空気中で粉砕した平均粒径が１２μｍの無定形Ａｌ−Ｃ
ｕ合金（Ｃｕ含量：２５原子％）粉末１部と一次粒子の
平均粒径０．０１μｍのファーネスブラック０．０５部
とをアセトニトリル中を分散媒として混合、乾燥したも
のを電極粉末として用い、（化５）で示されるカチオン
性界面活性剤をアセトニトリルに溶解した１０％のカチ
オン界面活性剤溶液と、平均粒径が８μｍのγーりん酸
ジルコニウム粉末と、Example 3 Amorphous Al-C with an average particle size of 12 μm pulverized in air
1 part of u-alloy (Cu content: 25 at%) powder and 0.05 part of furnace black with an average primary particle diameter of 0.01 μm were mixed in acetonitrile as a dispersion medium, dried, and used as an electrode powder. A 10% cationic surfactant solution prepared by dissolving a cationic surfactant represented by chemical formula 5) in acetonitrile, and γ-zirconium phosphate powder with an average particle size of 8 μm,
【００２８】[0028]
【化５】[C5]
【００２９】イオン性物質として過塩素酸リチウム（Ｌ
ｉＣｌＯ４）を用い、さらに、イオン伝導性固体電解質
としてＬｉ３ＮとＬｉＩとＢ２Ｏ３からなるリチウム化
合物を固形分重量として５％混合した以外は実施例１と
同様にして大きさが８０ｘ８０ｍｍ、厚さが１３５μｍ
のシート状電極組成物と、厚さが６５μｍのシート状電
解質を作製した。Lithium perchlorate (L
iClO4) was used, and a lithium compound consisting of Li3N, LiI, and B2O3 was further mixed as an ion-conductive solid electrolyte at a solid content of 5%.
A sheet-like electrode composition and a sheet-like electrolyte having a thickness of 65 μm were prepared.
【００３０】（比較例）ＬｉＣＦ３ＳＯ３をエチレンオ
キサイド１分子当り８分の１個溶解した平均分子量が４
８０万のポリエチレンオキサイドよりなる高分子固体電
解質と、実施例２と同様の電極粉末とを混合・乾燥して
厚さ３０５μｍのシート状の電極組成物を作製した。ま
た、厚さ１１５μｍのシート状電解質を作製した。
電極組成物の特性評価
実施例１〜３と比較例で得られた電極組成物を直径１０
ｍｍの円板に打ち抜き、特性試験用の試料とした。また
、各々の実施例で作製したシート状電解質を直径１０ｍ
ｍに打ち抜き電解セル構成用に用いた。電解質円板２枚
を、その間に参照電極用の線径が５０μｍの銀線を挟ん
で重ね電解質層を形成し、電解質層の片面に直径１０ｍ
ｍ、暑さ１ｍｍの金属リチウム円板を置き、もう一方の
面に電極円板を配置し、さらにその上下に白金円板を配
置した後、全体を５０ｋｇ／ｃｍ２の圧力で上下から加
圧した状態で、水分が２ｐｐｍ以下のアルゴンガス雰囲
気中で８０℃で３時間加熱し試験セルＡ（実施例１）、
試験セルＢ（実施例２）、試験セルＣ（実施例３）、試
験セルＤ（比較例）を組み立てた。電極円板を動作極、
金属リチウム極を対極、銀線を参照極として試験セルを
０Ｖを中心に±１．５Ｖの範囲で、電位を０→−１．５
→０Ｖ→＋１．５→０Ｖと直線的に掃引速度５ｍＶ／秒
で繰り返し変化さた。±０．６〜±１．１Ｖ付近に電流
のピークが現れ、ピーク電流値は充放電サイクルの進行
と共に変化した。２０、５０、１００、２００サイクル
後の還元電流のピークの電位と電流値を（表１）に示す
。(Comparative Example) The average molecular weight of LiCF3SO3 dissolved in one eighth of each molecule of ethylene oxide is 4.
A polymer solid electrolyte made of 800,000% polyethylene oxide and the same electrode powder as in Example 2 were mixed and dried to prepare a sheet-like electrode composition with a thickness of 305 μm. Further, a sheet-like electrolyte having a thickness of 115 μm was produced. Characteristic Evaluation of Electrode Compositions The electrode compositions obtained in Examples 1 to 3 and Comparative Examples were
A disk of mm was punched out and used as a sample for characteristic testing. In addition, the sheet-shaped electrolyte produced in each example was 10 m in diameter.
It was punched out and used for constructing an electrolytic cell. Two electrolyte disks are stacked with a silver wire with a wire diameter of 50 μm for a reference electrode sandwiched between them to form an electrolyte layer, and a diameter of 10 m is placed on one side of the electrolyte layer.
A metal lithium disk with a thickness of 1 mm was placed, an electrode disk was placed on the other side, and platinum disks were placed above and below it, and the whole was pressurized from above and below at a pressure of 50 kg/cm2. Test cell A (Example 1) was heated at 80°C for 3 hours in an argon gas atmosphere with moisture content of 2 ppm or less.
Test cell B (Example 2), test cell C (Example 3), and test cell D (Comparative example) were assembled. The electrode disk is the operating pole,
Using the metal lithium electrode as the counter electrode and the silver wire as the reference electrode, the potential of the test cell was changed from 0 to -1.5 in the range of ±1.5V around 0V.
→ 0 V → +1.5 → 0 V was repeatedly changed linearly at a sweep rate of 5 mV/sec. A current peak appeared around ±0.6 to ±1.1 V, and the peak current value changed as the charge/discharge cycle progressed. The peak potential and current value of the reduction current after 20, 50, 100, and 200 cycles are shown in (Table 1).
【００３１】[0031]
【表１】[Table 1]
【００３２】（表１）に示した結果から明らかなように
、本発明の電極組成物によれば、比較例の電極組成物に
較べ大きなピーク電流値が得られ、分極が小さい。また
、充放電サイクルの進行によるピーク電流値の低下も小
さい。また、電極組成物の機械強度を、長さ４０ｍｍ幅
５ｍｍの成形体を半径が５０ｍｍの曲面に沿って１秒間
に２回の割合で繰り返し折り曲げた際、破断するまでの
回数で評価したところ、８００回の折り曲げ試験後でも
破断することなく元の形状を保っていて、優れた機械強
度を有していることがわかる。As is clear from the results shown in Table 1, the electrode composition of the present invention provides a larger peak current value and smaller polarization than the electrode composition of the comparative example. Further, the decrease in peak current value due to progress of charge/discharge cycles is also small. In addition, the mechanical strength of the electrode composition was evaluated by the number of times it took to break when a molded body with a length of 40 mm and a width of 5 mm was repeatedly bent at a rate of 2 times per second along a curved surface with a radius of 50 mm. It can be seen that even after 800 bending tests, the original shape was maintained without breaking, indicating that it had excellent mechanical strength.
【００３３】[0033]
【発明の効果】以上の実施例の説明からも明らかなよう
に本発明によれば、エチレンオキサイド鎖および、また
はプロピレンオキサイド鎖を有するカチオン界面活性剤
の作用により電極材料粉末が均一に分散された電極面積
が大きくかつ均質な電極組成物を提供できる。このカチ
オン界面活性剤は、イオン交換性の層状化合物と複合体
を形成し、層状化合物の結晶の層間あるいは表面に高濃
度に保持されイオン伝導に有利な経路を形成し、電極組
成物内にあって電池反応の円滑な進行に必要なイオン伝
導の経路を提供する。本発明の電極組成物では、電子お
よびイオンの伝導経路が均一に形成され、その結果とし
て、分極の小さい電極組成物が得られる。Effects of the Invention As is clear from the description of the examples above, according to the present invention, the electrode material powder was uniformly dispersed by the action of the cationic surfactant having an ethylene oxide chain and/or a propylene oxide chain. It is possible to provide a homogeneous electrode composition with a large electrode area. This cationic surfactant forms a complex with the ion-exchangeable layered compound, is held at a high concentration between the layers or on the surface of the layered compound's crystals, and forms an advantageous path for ion conduction, and is present in the electrode composition. This provides the ionic conduction path necessary for the smooth progression of battery reactions. In the electrode composition of the present invention, electron and ion conduction paths are uniformly formed, and as a result, an electrode composition with low polarization can be obtained.
Claims (1)
合金粉末と、エチレンオキサイド鎖またはプロピレンオ
キサイド鎖のいずれかを有するカチオン界面活性剤、あ
るいはエチレンオキサイド鎖およびプロピレンオキサイ
ド鎖を有するカチオン界面活性剤と、イオン交換性の層
状化合物と、式ＭＸで表されるイオン性物質（ただし、
Ｍは電界の作用で固形電解質組成物内を移動する金属イ
オン、プロトン、アンモニウムイオンであり、Ｘは強酸
のアニオンである）を少なくとも含有する固形電極組成
物。1. Carbon powder, metallic aluminum or its alloy powder, and a cationic surfactant having either an ethylene oxide chain or a propylene oxide chain, or a cationic surfactant having an ethylene oxide chain and a propylene oxide chain; An ion exchange layered compound and an ionic substance represented by the formula MX (however,
M is a metal ion, proton, or ammonium ion that moves within the solid electrolyte composition under the action of an electric field, and X is an anion of a strong acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3007501A JP2929726B2 (en) | 1991-01-25 | 1991-01-25 | Solid electrode composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3007501A JP2929726B2 (en) | 1991-01-25 | 1991-01-25 | Solid electrode composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04248257A true JPH04248257A (en) | 1992-09-03 |
| JP2929726B2 JP2929726B2 (en) | 1999-08-03 |
Family
ID=11667531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3007501A Expired - Fee Related JP2929726B2 (en) | 1991-01-25 | 1991-01-25 | Solid electrode composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2929726B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017170366A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Polyether polymer composition and sheet |
| WO2017170367A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Polyether polymer composition |
-
1991
- 1991-01-25 JP JP3007501A patent/JP2929726B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017170366A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Polyether polymer composition and sheet |
| WO2017170367A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Polyether polymer composition |
| CN108884311A (en) * | 2016-03-31 | 2018-11-23 | 日本瑞翁株式会社 | Polyethers based polymer composition and sheet material |
| CN108884310A (en) * | 2016-03-31 | 2018-11-23 | 日本瑞翁株式会社 | Polyethers based polymer composition |
| JPWO2017170366A1 (en) * | 2016-03-31 | 2019-02-07 | 日本ゼオン株式会社 | Polyether polymer composition and sheet |
| JPWO2017170367A1 (en) * | 2016-03-31 | 2019-02-07 | 日本ゼオン株式会社 | Polyether polymer composition |
| US10851203B2 (en) | 2016-03-31 | 2020-12-01 | Zeon Corporation | Polyether polymer composition |
| US10907041B2 (en) | 2016-03-31 | 2021-02-02 | Zeon Corporation | Polyether polymer composition and sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2929726B2 (en) | 1999-08-03 |
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