JPH04272654A - Composition of solid electrode - Google Patents
Composition of solid electrodeInfo
- Publication number
- JPH04272654A JPH04272654A JP3032682A JP3268291A JPH04272654A JP H04272654 A JPH04272654 A JP H04272654A JP 3032682 A JP3032682 A JP 3032682A JP 3268291 A JP3268291 A JP 3268291A JP H04272654 A JPH04272654 A JP H04272654A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- solid
- ion
- electrode composition
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 abstract description 13
- 239000007784 solid electrolyte Substances 0.000 abstract description 13
- 230000010287 polarization Effects 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 150000001450 anions Chemical group 0.000 abstract description 2
- 230000005684 electric field Effects 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 3
- 239000004094 surface-active agent Substances 0.000 abstract 3
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 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
- 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
- 230000000052 comparative effect Effects 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002131 composite material 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
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910003480 inorganic solid 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal 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
- 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
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910017696 Ag6I4WO4 Inorganic materials 0.000 description 1
- 229910017719 AgI—Ag2O—MoO3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910016517 CuI—Cu2O—MoO3 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910002335 LaNi5 Inorganic materials 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910010823 LiI—Li2S—B2S3 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910008447 Li—Al Inorganic materials 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
- 229910019445 Mg(ClO4) Inorganic materials 0.000 description 1
- 229910020042 NbS2 Inorganic materials 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910002781 RbAg4I5 Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- RGJSWMPPIHQBPC-UHFFFAOYSA-N [V+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [V+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] RGJSWMPPIHQBPC-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 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-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 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
- 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
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002892 organic cations Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 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
- 230000032258 transport Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-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、セ
ンサ、表示素子、記録素子等の電気化学素子に用いられ
る固形電極組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrode composition for use in electrochemical devices such as batteries, capacitors, sensors, display devices, and recording devices.
【０００２】0002
【従来の技術】一般の電気化学素子においては、従来の
液体の電解質に代えて固体の電解質を用いることにより
液漏れがなく、小形薄形化された電池や電気二重層キャ
パシタ等の固体の電気化学素子を得ることができる。[Prior Art] In general electrochemical devices, a solid electrolyte is used instead of a conventional liquid electrolyte, so there is no leakage, and solid electrolytes such as small and thin batteries and electric double layer capacitors are used. Chemical elements can be obtained.
【０００３】しかしながら、これらの電気化学素子は弾
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、破損しやすいという欠
点がある。このよう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
Ｔｒａｎｓ−ｐｏｒｔ ｉｎ Ｓｏｌｉｄ” Ｐ．
Ｖａｎｉｓｈｓｔａｅｔ．ａｌ．， Ｅｄｓ． Ｐ．
１３１（１９７９） Ｎｏｒｔｈ Ｈｏｌａｎｄ Ｐｕ
ｂｌｉｓ−ｈｉｎｇ Ｃｏ．） 。However, since these electrochemical devices are constructed of solid materials lacking in elasticity, they have the drawback of being extremely brittle and easily damaged by mechanical shock. In order to solve these problems, a solid polymer electrolyte made of polyethylene oxide (PEO) and an alkali metal salt has been proposed ("Fast Ion").
Trans-port in Solid” P.
Vanishstate. al. , Eds. P.
131 (1979) North Holland Pu
blis-hing Co. ).
【０００４】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。そして、これらの高分子電解質と五酸
化バナジウム等の無機化合物よりなる電極材料またはポ
リアニリン等の有機化合物よりなる電極材料と混合して
固体の電極組成物とし、高分子電解質を介して電極組成
物を接合することで固体状態の電池が現在提案されてい
る。[0004] 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. Then, these polymer electrolytes are mixed with an electrode material made of an inorganic compound such as vanadium pentoxide or an electrode material made of an organic compound such as polyaniline to form a solid electrode composition, and the electrode composition is mixed through the polymer electrolyte. Solid-state batteries are currently being proposed by bonding.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記従
来のこれまで得られている電極組成物では必ずしも電極
材料と高分子電解質とが均質に分散混合されておらず、
イオン伝導と電子伝導のためのネットワークが十分でな
く、例えばＪｏｕｒｎａｌ ｏｆ Ｐｏｗｄｅｒ Ｓｏ
ｕｒｃｅｓ， ２８巻， ３９７〜４０８頁（１９８７
年）に述べられているように、ＬｉＣＦ３ＳＯ３を溶解
したホ゜リエチレンオキサイト゛よりなる高分子固体電
解質（ＳＰＥ）と、リチウム負極と、アモルファスＶ２
Ｏ５とＳＰＥとカーホ゛ンフ゛ラックの配合物よりなる
正極とから構成された電池の正極の利用率は、約１０％
（放電電流密度：０．３３ ｍＡ／ｃｍ２， 温度：２
０℃）と低く電極材料が十分に利用されていないという
課題があった。[Problems to be Solved by the Invention] However, in the above-mentioned conventional electrode compositions, the electrode material and the polymer electrolyte are not necessarily homogeneously dispersed and mixed.
The network for ionic and electronic conduction is insufficient, for example, Journal of Powder So
urces, vol. 28, pp. 397-408 (1987
As described in 2010), a solid polymer electrolyte (SPE) made of polyethylene oxide in which LiCF3SO3 is dissolved, a lithium negative electrode, and an amorphous V2
The utilization rate of the positive electrode of a battery composed of a positive electrode made of a combination of O5, SPE, and carbon fiber is approximately 10%.
(Discharge current density: 0.33 mA/cm2, temperature: 2
There was a problem that the temperature was low (0°C) and the electrode materials were not fully utilized.
【０００６】本発明は上記課題を解決するものであり、
均質な成形性の良いイオン伝導性、電子伝導性のともに
優れた固形電極組成物を提供することを目的とする。[0006] The present invention solves the above problems,
The purpose of the present invention is to provide a solid electrode composition that is homogeneous, has good moldability, and has excellent ionic conductivity and electronic conductivity.
【０００７】[0007]
【課題を解決するための手段】本発明は上記目的を達成
するために、電極活物質と、必要により導電材と、エチ
レンオキサイド（ＥＯ）鎖とプロピレンオキサイド（Ｐ
Ｏ）鎖の少なくとも一方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）とを少なくとも含
有する電極組成物であり、さらに、電極組成物内のイオ
ン伝導性を上げる目的でイオン伝導性の粒子を含有する
ことができる。[Means for Solving the Problems] In order to achieve the above object, the present invention comprises an electrode active material, an electrically conductive material if necessary, an ethylene oxide (EO) chain and a propylene oxide (P
O) a cationic surfactant having at least one chain, an ion-exchange layered compound, and an ionic substance represented by the formula MX (where M is a metal ion that moves within the solid electrode composition under the action of an electric field); , a proton, an ammonium ion, and X is an anion of a strong acid), and further contains ion conductive particles for the purpose of increasing the ion conductivity within the electrode composition. Can be done.
【０００８】[0008]
【作用】したがって本発明によれば、イオン性物質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
複合体を形成して層状化合物の結晶の層間または表面に
高濃度に保持されイオン伝導に有利な経路を形成し、ま
た電極活物質の粉末と、必要により導電材の粉末は、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
状化合物と均一に混和され、電池反応に必要な電子およ
びイオンの伝導経路を形成し、さらにイオン伝導性粉末
の添加混合に際してはその粉末の凝集を防止し、溶媒と
イオン交換性の層状化合物および電子伝導性の電極活物
質および導電材との均一な混合分散を可能にするため、
高い電子・イオン伝導性と均質性を得ることができる。
その結果、分極の小さい、かつ電極利用率の高い電極組
成物となる。また、カチオン界面活性剤のエチレンオキ
サイド鎖とイオン交換性の層状化合物のマイクロポーラ
ス構造とが絡まって良好な成形性と十分な機械強度が付
与される。[Operation] Therefore, according to the present invention, the ionic substance MX
forms a complex with a cationic surfactant and an ion-exchangeable layered compound, and is held at a high concentration between the layers or on the surface of the crystal of the layered compound, forming an advantageous path for ion conduction, and also forms a complex with the electrode active material powder. And, if necessary, the conductive material powder is uniformly mixed with the solvent and the ion-exchange layered compound by the action of the cationic surfactant, forming the electron and ion conduction paths necessary for the battery reaction, and further improving the ionic conductivity. When adding and mixing the powder, in order to prevent the powder from agglomerating and to enable uniform mixing and dispersion of the solvent, the ion exchange layered compound, the electron conductive electrode active material, and the conductive material.
High electron/ion conductivity and homogeneity can be obtained. As a result, an electrode composition with low polarization and high electrode utilization is obtained. In addition, the ethylene oxide chain of the cationic surfactant and the microporous structure of the ion-exchangeable layered compound are entangled to provide good moldability and sufficient mechanical strength.
【０００９】[0009]
【実施例】以下、本発明の一実施例について、詳細に説
明する。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。[Embodiment] An embodiment of the present invention will be described in detail below. Further, in the following examples, parts, percentages, and ratios represent parts by weight, percentages by weight, and weight ratios unless otherwise specified.
【００１０】本発明における電極活物質および導電材と
しては、金属銅、金属銀、金属リチウム等の単体金属、
Ｌｉ−Ａｌ， ＬａＮｉ５ 等の合金、硫化銅、硫化銀
、銅シュブレル化合物、銀シュブレル化合物、硫化チタ
ン、硫化ニオブ、硫化モリブデン等の金属硫化物、二酸
化マンガン、酸化バナジウム、酸化コバルト、酸化クロ
ム等の金属酸化物、塩化銀、ヨウ化鉛、フッ化カーボン
等のハロゲン化物または活性炭、黒鉛、カーボンブラッ
ク等の炭素材料など常温で固体状の材料を使用すること
ができる。また形状としては平均粒径が１μｍ以下の超
微粒子から数１０μｍの粒子のものまで何れも用いるこ
とができる。[0010] The electrode active material and conductive material in the present invention include elemental metals such as metallic copper, metallic silver, metallic lithium, etc.
Alloys such as Li-Al and LaNi5, metal sulfides such as copper sulfide, silver sulfide, copper Chevrel compounds, silver Chevrel compounds, titanium sulfide, niobium sulfide, and molybdenum sulfide, manganese dioxide, vanadium oxide, cobalt oxide, chromium oxide, etc. Materials that are solid at room temperature can be used, such as metal oxides, halides such as silver chloride, lead iodide, and carbon fluoride, or carbon materials such as activated carbon, graphite, and carbon black. Furthermore, any shape can be used ranging from ultrafine particles with an average particle size of 1 μm or less to particles with an average particle size of several tens of μm.
【００１１】本発明におけるＥＯ鎖とＰＯ鎖の少なくと
も一方を有するカチオン界面活性剤としては、例えば下
式（化１）または（化２）で示されるものが挙げられる
。[0011] Examples of the cationic surfactant having at least one of an EO chain and a PO chain in the present invention include those represented by the following formula (Formula 1) or (Formula 2).
【００１２】0012
【化１】[Chemical formula 1]
【００１３】[0013]
【化２】[Case 2]
【００１４】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％が好ましい。The amount of the cationic surfactant added is preferably 0.5 to 20% based on the total amount of the solid electrode composition.
【００１５】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， ＮａＩ， ＮａＳＣＮ， ＮａＢｒ， ＫＩ，
ＡｇＮＯ３， ＣｕＣｌ２， Ｍｇ（ＣｌＯ４）２，Ｚ
ｎＣｌ２， ＡｌＣｌ３ 等の可溶性の塩が用いられる
。[0015] There are no particular restrictions on the ionic substance, but LiI, LiClO4, LiCF3SO3, L
iPF6, LiBF4, LiSCN, LiAsF
6, NaI, NaSCN, NaBr, KI,
AgNO3, CuCl2, Mg(ClO4)2, Z
Soluble salts such as nCl2, AlCl3, etc. are used.
【００１６】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
ト等のけい酸塩を含む粘土鉱物、りん酸ジルコニウム、
りん酸チタニウム等のりん酸エステル、バナジン酸、ア
ンチモン酸、タングステン酸、またはそれらを第４級ア
ンモニウム塩等の有機カチオンまた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 the ion exchange layered compound include clay minerals containing silicates such as montmorillonite, hectorite, saponite, and smectite, zirconium phosphate,
Examples include phosphoric acid esters such as titanium phosphate, vanadate, antimonic acid, tungstic acid, or those modified with organic cations such as quaternary ammonium salts or organic polar compounds such as ethylene oxide and propylene oxide.
【００１７】さらに本発明の固形電極組成物の中に下記
のイオン伝導性の粉末を添加することも可能である。す
なわちイオン伝導性の粉末としては、ＭｅＣｕ４Ｉ２−
ｘＣｌ３＋ｘ （ｘ＝０．２５−１．０， Ｍｅ＝ Ｒ
ｂ， Ｋ， ＮＨ４ またはそれらを混合したもの）や
ＣｕＩ−Ｃｕ２Ｏ−ＭｏＯ３ガラス等の銅イオン伝導性
固体電解質、ＲｂＡｇ４Ｉ５ 、Ａｇ３Ｓｉ、 ＡｇＩ
−Ａｇ２Ｏ−ＭｏＯ３ガラス、Ａｇ６Ｉ４ＷＯ４ 等の
銀イオン伝導性固体電解質、ＬｉＩ、ＬｉＩ・Ｈ２Ｏ、
Ｌｉ−β−Ａｌ２Ｏ３、ＬｉＩ−Ｌｉ２Ｓ−Ｂ２Ｓ３、
ＰＥＯ−ＬｉＣＦ３ＳＯ３ 等のリチウムイオン伝導性
固体電解質、Ｈ３Ｍｏ１２ＰＯ４０・２９Ｈ２Ｏ、Ｈ３
Ｗ１２ＰＯ４０・２９Ｈ２Ｏ等のプロトン伝導性固体電
解質を用いることができる。その形状としては平均粒径
が１μｍ以下の超微粒子から数１０μｍの粒子のものま
で何れも用いることができる。上記のイオン伝導性の粉
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, it is also possible to add the following ion conductive powder to the solid electrode composition of the present invention. That is, as the ion conductive powder, MeCu4I2-
xCl3+x (x=0.25-1.0, Me=R
copper ion conductive solid electrolytes such as CuI-Cu2O-MoO3 glass, RbAg4I5, Ag3Si, AgI
-Ag2O-MoO3 glass, silver ion conductive solid electrolyte such as Ag6I4WO4, LiI, LiI・H2O,
Li-β-Al2O3, LiI-Li2S-B2S3,
Lithium ion conductive solid electrolyte such as PEO-LiCF3SO3, H3Mo12PO40・29H2O, H3
A proton conductive solid electrolyte such as W12PO40.29H2O can be used. Any shape can be used, ranging from ultrafine particles with an average particle size of 1 μm or less to particles with an average particle size of several tens of μm. There is no limit to the amount of the ion conductive powder added as long as the moldability of the solid electrode composition is not impaired.
【００１８】本発明の固形電極組成物は次のようにして
得られる。イオン性物質を１から５０％溶解した溶剤に
イオン交換性の層状化合物の粉末を１〜５０％となるよ
うに加え、次にＥＯ鎖ＰＯ鎖の少なくとも一方を有する
カチオン界面活性剤をスラリー全体に対して０．１〜２
０％の割合になるように加え、ディスパーサ等の混合粉
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。 また、イオン性物質を１か
ら５０％溶解した溶剤にＥＯ鎖とＰＯ鎖の少なくとも一
方を有するカチオン界面活性材を０．１〜２０％含むカ
チオン界面活性材溶液に、電極活物質の粉末および必要
に応じ電極活物質の粉末と導電材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。次に、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好ましい。このようにし
て得られた電極組成物スラリーを、フッ素樹脂板とかナ
イロンメッシュシートとかの支持体上に流延または塗布
して成形した後、溶剤を一部または全部散逸させること
によって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。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 substance is dissolved, and then add a cationic surfactant having at least one of an EO chain and a PO chain to the entire slurry. 0.1-2 against
The electrolyte slurry having a solid content of 5 to 95% is prepared by pulverizing and mixing using a mixer such as a disperser. In addition, the powder of the electrode active material and the necessary Depending on the conditions, a pre-mixed powder of electrode active material powder and conductive material 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 fluororesin plate or a nylon mesh sheet and shaped, and then the solid electrolyte composition is formed by dissipating some or all of the solvent. can be obtained. 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.
【００１９】必要に応じ、これらの工程は相対湿度が４
０％以下の乾燥雰囲気中で行われる。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
ケトン等のケトン系溶剤、ｎ−ヘキサン、ｎ−ヘプタン
、ｎ−オクタン、シクロヘキサン等の飽和炭化水素系溶
剤、ベンゼン、トルエン、キシレン等の芳香族系溶剤、
酢酸エチル、酢酸プチル、プロピレンカーボネート等の
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等のアルコール系溶剤、アセトニト
リル等のニトリル類、あるいは水が用いられる。If necessary, these steps may be carried out at a relative humidity of 4
It is carried out in a dry atmosphere of 0% or less. Examples of solvents 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 aromatic solvents such as benzene, toluene, and xylene. solvent,
Ester solvents such as ethyl acetate, butyl acetate, and propylene carbonate, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, glycerin, and polyethylene glycol, nitrites such as acetonitrile, or water are used.
【００２０】（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) The cationic surfactant shown in (Chemical formula 3) was dissolved in acetonitrile to prepare a 20% cationic surfactant solution.
【００２１】[0021]
【化３】[Chemical formula 3]
【００２２】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
拌混合し電解質スラリーを得た。 次に、カチオン界
面活性剤溶液に平均粒径が６μｍの硫化ニオブ粉末（Ｎ
ｂＳ２）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。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. Obtained. Next, niobium sulfide powder (N
bS2) was added so that the solid content was 50%, and 40
The mixture was mixed at ℃ for 24 hours to obtain an electrode slurry.
【００２３】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
リーを平滑なフッ素樹脂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で、大きさ
８０ｘ８０ｍｍ、厚さ１５０μｍのシート状の固形
電極組成物を得た。また、電池を構成するために、電解
質スラリーのみを同様にして塗布乾燥して大きさ８０ｘ
８０ｍｍ、厚さ８０ミクロンの電解質シートを作製した
。An electrode composition slurry was obtained by mixing the electrolyte slurry and the electrode slurry in an alumina ball mill for 24 hours so that the solid content ratio was 1:2. After applying the electrode composition slurry on a smooth fluororesin plate using a doctor blade, it was heated for 1 hour in a dry argon stream at 130°C.
By drying for an hour and further vacuum drying for 5 hours, a sheet-like solid electrode composition with a size of 80 x 80 mm and a thickness of 150 μm was obtained. In addition, in order to construct a battery, only the electrolyte slurry was applied and dried in the same manner, and a size of 80×
An electrolyte sheet having a length of 80 mm and a thickness of 80 microns was prepared.
【００２４】（実施例２）電極活物質としてバナジウム
ブトキサイドの加水分解により得た平均粒径が０．５μ
ｍのバナジウム酸化物粉末１部と平均粒径が０．０２μ
ｍのファーネスブラック０．１部とをエタノールを分散
媒として混合乾燥したものを電極粉末として用い、（化
４）で示されるカチオン性界面活性剤と平均粒径が５μ
ｍ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（ＬｉＣＦ３ＳＯ３）とを
用いた以外は実施例１と同様にして、厚さが１３５μｍ
のシート状の固形電極組成物と厚さが５０μｍのシート
状電解質を作製した。(Example 2) An electrode active material obtained by hydrolysis of vanadium butoxide with an average particle size of 0.5μ
1 part of vanadium oxide powder with an average particle size of 0.02μ
The electrode powder was prepared by mixing and drying 0.1 part of furnace black with ethanol as a dispersion medium, and a cationic surfactant represented by (Chemical formula 4) and an average particle size of 5 μm.
A montmorillonite powder of 135 μm in thickness was prepared in the same manner as in Example 1 except that lithium trifluorosulfonate (LiCF3SO3) was used as the ionic substance.
A sheet-like solid electrode composition and a sheet-like electrolyte having a thickness of 50 μm were prepared.
【００２５】[0025]
【化４】[C4]
【００２６】実施例３
炭酸リチウムと炭酸マンガンの混合物を加熱分解するこ
とにより得た平均粒径７ミクロンのリチウム・マンガン
複合酸化物（ＬｉＭｎ２Ｏ４）粉末１部と平均粒径０．
０２ミクロンのファーネスブラック０．２部との混合物
を電極活物質として用い、（化５）で示されるカチオン
性界面活性剤と、平均粒径が８μｍのγーりん酸ジルコ
ニウム粉末と、イオン性物質として過塩素酸リチウム（
ＬｉＣｌＯ４）を用い、さらに、イオン伝導性の固体電
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１８０
μｍのシート状の固形電極組成物と、厚さが７０μｍの
シート状電解質を作製した。Example 3 One part of lithium-manganese composite oxide (LiMn2O4) powder with an average particle size of 7 microns obtained by thermally decomposing a mixture of lithium carbonate and manganese carbonate and 1 part of lithium-manganese composite oxide (LiMn2O4) powder with an average particle size of 0.
A cationic surfactant represented by (Chemical formula 5), γ-zirconium phosphate powder with an average particle size of 8 μm, and an ionic substance were used as an electrode active material. as lithium perchlorate (
LiClO4) was used, and a lithium compound consisting of Li3N, LiI, and B2O3 was used as an ion-conductive solid electrolyte, and 5% of the solid content was mixed.
A sheet-like solid electrode composition having a thickness of 70 μm and a sheet-like electrolyte having a thickness of 70 μm were prepared.
【００２７】[0027]
【化５】[C5]
【００２８】比較例
ＬｉＣＦ３ＳＯ３をエチレンオキサイド一分子当り８分
の１個溶解した平均分子量が４８０万のポリエチレンオ
キサイドよりなる高分子固体電解質と、実施例２と同様
の電極活物質とを混合・乾燥することで厚さ１３５μｍ
シート状の固形電極組成物を作製した。また、厚さ５０
μｍのシート状電解質を作製した。Comparative Example A solid polymer electrolyte made of polyethylene oxide having an average molecular weight of 4.8 million, in which one-eighth of LiCF3SO3 is dissolved per molecule of ethylene oxide, and the same electrode active material as in Example 2 are mixed and dried. Therefore, the thickness is 135μm
A sheet-shaped solid electrode composition was produced. Also, the thickness is 50
A sheet-like electrolyte of μm size was produced.
【００２９】固形電極組成物の特性評価実施例１〜３と
比較例で得られた固形電極組成物を用いて直径１０ｍｍ
の円板を打ち抜き、特性試験用の試料とした。また各々
の実施例において作製したシート状電解質を直径１０ｍ
ｍに打ち抜き電池構成用に用いた。電解質円板の一方の
面に厚さ２ｍｍ、直径１０ｍｍの金属リチウム円板を配
置し、他方の面に固形電極組成物の円板を配置し、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２ｐｐ
ｍ以下のアルゴンガス雰囲気中で８０℃で３時間加熱し
、試験電池Ａ（実施例１）、試験電池Ｂ（実施例２）、
試験電池Ｃ（実施例３）、試験電池Ｂ’（比較例）を各
々１０個づつ組み立てた。試験電池を３．５Ｖの一定電
圧で１７時間充電した後、０．０５ｍＡの一定電流で１
０秒間放電を行い、放電直前および放電直後の電池電圧
の差（分極）を測定し１０個の電池について平均値と標
準偏差値を求めた。また、同じ電流値で０．３ボルトま
で連続放電を行い放電容量を求め、理論容量（１００％
）に対する電極活物質の利用率を求めた。分極値の結果
を（表１）に、電極の利用率を（表２）に示す。電極利
用率は、ＮｂＳ２、 Ｖ２Ｏ５、ＬｉＭｎ２Ｏ４ １モ
ルに対し、Ｌｉが１モル反応した場合を１００％として
評価した。Characteristic evaluation of solid electrode compositions Using the solid electrode compositions obtained in Examples 1 to 3 and Comparative Examples,
A disk was punched out and used as a sample for characteristic testing. In addition, the sheet electrolyte prepared in each example was 10 m in diameter.
It was punched out and used for battery construction. A metal lithium disk with a thickness of 2 mm and a diameter of 10 mm is placed on one side of the electrolyte disk, a disk of solid electrode composition is placed on the other side, and platinum disks are placed above and below it, and then, Total weight: 50kg/
Water content is 2pp when pressurized from above and below with cm2 pressure.
Heated at 80° C. for 3 hours in an argon gas atmosphere of 300 m or less to produce test battery A (Example 1), test battery B (Example 2),
Ten test batteries C (Example 3) and ten test batteries B' (Comparative example) were assembled. After charging the test battery at a constant voltage of 3.5V for 17 hours, it was charged at a constant current of 0.05mA for 1
Discharge was performed for 0 seconds, and the difference (polarization) between battery voltages immediately before and after discharge was measured, and the average value and standard deviation value were determined for the 10 batteries. In addition, the discharge capacity was determined by continuously discharging up to 0.3 volts at the same current value, and the theoretical capacity (100%
) was calculated for the utilization rate of the electrode active material. The results of the polarization values are shown in (Table 1), and the utilization rates of the electrodes are shown in (Table 2). The electrode utilization rate was evaluated with the case where 1 mole of Li reacted with 1 mole of NbS2, V2O5, and LiMn2O4 as 100%.
【００３０】[0030]
【表１】[Table 1]
【００３１】[0031]
【表２】[Table 2]
【００３２】上記実施例および（表１）、（表２）に示
した結果から明らかなように、本実施例による固形電極
組成物は、電極利用率が３０％以上あり、また分極の標
準偏差値は小さく電極活物質と固体電解質とが均一に混
合された均質な電極組成物であることを示している。As is clear from the results shown in the above examples and Tables 1 and 2, the solid electrode composition according to this example has an electrode utilization rate of 30% or more and a standard deviation of polarization. The value is small, indicating a homogeneous electrode composition in which the electrode active material and solid electrolyte are evenly mixed.
【００３３】また、本実施例の固形電極組成物の機械強
度を、長さ４０ｍｍ幅５ｍｍの成形体を用いて半径が５
０ｍｍ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、破断に至るまでの回数で評価したところ、
いずれの固形電極組成物も５０００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おり、優れた機
械強度を有していることがわかった。In addition, the mechanical strength of the solid electrode composition of this example was measured using a molded body with a length of 40 mm and a width of 5 mm.
When repeatedly bent along a 0 mm curved surface at a rate of 2 times per second, evaluation was made based on the number of times it took to break.
It was found that all solid electrode compositions maintained their original shapes without breaking even after 5,000 bending tests, and had excellent mechanical strength.
【００３４】[0034]
【発明の効果】上記実施例より明らかなように本発明に
よれば、エチレンオキサイド鎖とプロピレンオキサイド
鎖の少なくとも一方を有する特定のカチオン界面活性剤
の作用により、電極活物質および導電材が均一に分散さ
れた均質な固形電極組成物を提供することができる。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または表面に高
濃度に保持されイオン伝導に有利な経路を形成し、固形
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
オン伝導の経路を形成でき、また電子およびイオンの伝
導経路が均一に形成されるため、電極利用率の高い、分
極の小さい、かつ均一な特性を得ることができる。Effects of the Invention As is clear from the above examples, according to the present invention, the electrode active material and the conductive material are uniformly coated by the action of a specific cationic surfactant having at least one of an ethylene oxide chain and a propylene oxide chain. A dispersed and homogeneous solid electrode composition can be provided. This cationic surfactant forms a complex with the ion-exchangeable layered compound and is retained at a high concentration between the layers or on the surface of the layered compound's crystals, forming an advantageous path for ion conduction, and is present in the solid electrode composition. The ionic conduction path necessary for the smooth progression of battery reactions can be formed by using this method, and the conduction paths for electrons and ions are formed uniformly, resulting in high electrode utilization, low polarization, and uniform characteristics. Can be done.
Claims (2)
ロピレンオキサイド鎖の少なくとも一方を有するカチオ
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）
とを少なくとも含有することを特徴とする固形電極組成
物。Claim 1: an electrode active material, a cationic surfactant having at least one of an ethylene oxide chain and a propylene oxide chain, an ion exchange layered compound, and a compound having the formula MX.
An ionic substance represented by
A solid electrode composition comprising at least the following.
組成物。2. The solid electrode composition according to claim 1, which contains a conductive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3032682A JPH04272654A (en) | 1991-02-27 | 1991-02-27 | Composition of solid electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3032682A JPH04272654A (en) | 1991-02-27 | 1991-02-27 | Composition of solid electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04272654A true JPH04272654A (en) | 1992-09-29 |
Family
ID=12365648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3032682A Pending JPH04272654A (en) | 1991-02-27 | 1991-02-27 | Composition of solid electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04272654A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100763891B1 (en) * | 2005-12-01 | 2007-10-05 | 삼성에스디아이 주식회사 | Anode active material and lithium battery using the same |
| JP2017162597A (en) * | 2016-03-08 | 2017-09-14 | 富士フイルム株式会社 | Electrode material, electrode sheet for all-solid-state secondary battery and all-solid-state secondary battery using the electrode material, and method of manufacturing electrode sheet for all-solid-state secondary battery and all-solid-state secondary battery |
| JP2021044225A (en) * | 2019-09-13 | 2021-03-18 | 株式会社東芝 | Electrode, rechargeable battery, battery pack, and vehicle |
-
1991
- 1991-02-27 JP JP3032682A patent/JPH04272654A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100763891B1 (en) * | 2005-12-01 | 2007-10-05 | 삼성에스디아이 주식회사 | Anode active material and lithium battery using the same |
| US8283070B2 (en) | 2005-12-01 | 2012-10-09 | Samsung Sdi Co., Ltd. | Anode active material and lithium battery using the same |
| JP2017162597A (en) * | 2016-03-08 | 2017-09-14 | 富士フイルム株式会社 | Electrode material, electrode sheet for all-solid-state secondary battery and all-solid-state secondary battery using the electrode material, and method of manufacturing electrode sheet for all-solid-state secondary battery and all-solid-state secondary battery |
| JP2021044225A (en) * | 2019-09-13 | 2021-03-18 | 株式会社東芝 | Electrode, rechargeable battery, battery pack, and vehicle |
| US11515531B2 (en) | 2019-09-13 | 2022-11-29 | Kabushiki Kaisha Toshiba | Electrode, secondary battery, battery pack, and vehicle |
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