JP4131422B2 - 非水電解液及びそれを含む二次電池 - Google Patents
非水電解液及びそれを含む二次電池 Download PDFInfo
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- JP4131422B2 JP4131422B2 JP2007544125A JP2007544125A JP4131422B2 JP 4131422 B2 JP4131422 B2 JP 4131422B2 JP 2007544125 A JP2007544125 A JP 2007544125A JP 2007544125 A JP2007544125 A JP 2007544125A JP 4131422 B2 JP4131422 B2 JP 4131422B2
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- positive electrode
- aluminum
- secondary battery
- aqueous electrolyte
- active material
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 45
- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- 150000003839 salts Chemical class 0.000 claims description 49
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 40
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 description 38
- -1 hydroxide ions Chemical class 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004693 imidazolium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 229910018365 Al0.5Sc0.5(MoO4)3 Inorganic materials 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 description 1
- YXJSMCZTRWECJF-UHFFFAOYSA-N 1-butyl-1-ethylpyrrolidin-1-ium Chemical compound CCCC[N+]1(CC)CCCC1 YXJSMCZTRWECJF-UHFFFAOYSA-N 0.000 description 1
- XHKAHZUQTSMSDV-UHFFFAOYSA-N 1-butyl-1-methylpiperazin-1-ium Chemical compound CCCC[N+]1(C)CCNCC1 XHKAHZUQTSMSDV-UHFFFAOYSA-N 0.000 description 1
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- CMLKRBXRFRWXTB-UHFFFAOYSA-N 1-butyl-3-ethylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC(CC)=C1 CMLKRBXRFRWXTB-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- RQQSKNIQUGQEHJ-UHFFFAOYSA-N 1-ethyl-1-methylpiperazin-1-ium Chemical compound CC[N+]1(C)CCNCC1 RQQSKNIQUGQEHJ-UHFFFAOYSA-N 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- OIDIRWZVUWCCCO-UHFFFAOYSA-N 1-ethylpyridin-1-ium Chemical compound CC[N+]1=CC=CC=C1 OIDIRWZVUWCCCO-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- HLVHWHHMXLULJM-UHFFFAOYSA-N 2-butyl-3-methyl-1h-imidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCC=1NC=C[N+]=1C HLVHWHHMXLULJM-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-O 3-butyl-1h-imidazol-3-ium Chemical compound CCCCN1C=C[NH+]=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-O 0.000 description 1
- 229910018117 Al-In Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018170 Al—Au Inorganic materials 0.000 description 1
- 229910018229 Al—Ga Inorganic materials 0.000 description 1
- 229910018456 Al—In Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018507 Al—Ni Inorganic materials 0.000 description 1
- 229910018525 Al—Pt Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical class C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- NINOVVRCHXVOKB-UHFFFAOYSA-N dialuminum;dioxido(dioxo)chromium Chemical compound [Al+3].[Al+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O NINOVVRCHXVOKB-UHFFFAOYSA-N 0.000 description 1
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-O hydron piperazine Chemical compound [H+].C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-O 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical class C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
- H01M2300/0022—Room temperature molten salts
-
- 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
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- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
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Description
非特許文献1に開示されているように、アルミニウム空気電池は、酸化還元電位が高く、負極上で電解液である水の電気分解が起こり、水素を発生してしまう。また、水酸化物イオン(OH−)を可動イオンとするため、負極では水酸化アルミニウムが生成し、水に溶けにくいことから負極に放電阻害物質となる等の問題がある。これらの問題は、水系の電解液、可動イオンがOH−であることに起因している。
さらに、AlCl3以外のAl塩を用いてAl3+を可動イオンとする非水電解液も開示されている。(例えば特許文献4)
また、可動イオンをリチウムイオンとする非水電解液を有し、アルミニウムイオンを吸蔵・放出する物質として炭素材料を用いる電池が開示されている。(例えば特許文献5,6)
一方、Al2(WO4)3等を具体例とする3価の金属イオンを可動イオンとする固体電解質が開示されている。これらは、高密度の電荷移動が可能であることから、一部ガスセンサー又は固体二次電池の電解質への応用について開示されている。(例えば特許文献7,8,9)
Al2(WO4)3等と同じ結晶構造をもつ物質が低熱膨張材料として知られている。(例えば特許文献10)
そのほかにも、M2(MoO4)3(但し、MはAl等の第13族に含まれる元素群から選択される少なくとも1種を示す。)で示される化合物からなる非水電解質二次電池用電極活物質が知られている。(例えば特許文献11)
さらに、一般的なAlとW、Moとの複合酸化物として、AlxWO3で示されるタングステンブロンズ構造をもつ化合物が開示されている。(例えば非特許文献2,3)
1. Al(CF3SO3)3を含む電解質と4級アンモニウム塩の常温溶融塩とを含む非水電解液であって、
前記4級アンモニウム塩が、下記一般式(1)又は(2)
で示される化合物の少なくとも1種である、非水電解液。
2. アルキル基が炭素数1〜6のアルキル基である、前記項1に記載の非水電解液。
3. さらに非水有機溶媒を含む、前記項1に記載の非水電解液。
4. 前記非水有機溶媒が、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネートから選択される少なくとも1種を含む、前記項3に記載の非水電解液。
5. 負極、非水電解液及び正極を含む二次電池であって、前記非水電解液が前記項1に記載の非水電解液である二次電池。
6. 前記負極における活物質がアルミニウム及びアルミニウム合金の少なくとも1種である、前記項5に記載の二次電池。
7. 前記正極における活物質が、下記一般式(3)
(AlxM1−x)2(M’O4)3 (3)
(但し、MはM2 aM3 bM4 cであって、M2はMg、Ca、Sr及びBaから選択される2価の金属元素の少なくとも1種、M3はSc、Y、Ga及びInから選択される3価の金属元素の少なくとも1種、M4はZr及びHfから選択される4価の金属元素の少なくとも1種を示す。M’はW又はMoを含む6価の金属元素を示す。0≦a<1、0≦b<1、c=a、0<x≦1、(2a/(1−x))+(3b/(1−x))+(4c/(1−x))=3)
で示される酸化物である、前記項5に記載の二次電池。
本発明の非水電解液は、Al(CF3SO3)3を含む電解質と4級アンモニウム塩の常温溶融塩とを含む非水電解液であって、
前記4級アンモニウム塩が、下記一般式(1)又は(2)
で示される化合物の少なくとも1種であることを特徴とする。
2.二次電池
本発明は、負極、非水電解液及び正極を含む二次電池であって、非水電解液として本発明の非水電解液を用いる二次電池(特にアルミニウム二次電池)を包含する。
(AlxM1−x)2(M’O4)3 (3)
(但し、MはM2 aM3 bM4 cであって、M2はMg、Ca、Sr及びBaから選択される2価の金属元素の少なくとも1種、M3はSc、Y、Ga及びInから選択される3価の金属元素の少なくとも1種、M4はZr及びHfから選択される4価の金属元素の少なくとも1種を示す。M’はW又はMoを含む6価の金属元素を示す。0≦a<1、0≦b<1、c=a、0<x≦1、(2a/(1−x))+(3b/(1−x))+(4c/(1−x))=3)
で示される酸化物を正極活物質として用いることが望ましい。
(実施例1)
Al(CF3SO3)3の各種常温溶融塩への溶解性を評価した。常温溶融塩に対して、それぞれ50mM(Mはmol/Lを示す)のAl(CF3SO3)3を加え、24時間攪拌を行った後、その状態(未溶解固形分の有無)を肉眼で確認した。
次に(実施例1)でAl塩を良く溶解したサンプル3,7,9について、濃度を変えて溶解度を評価した。十分に溶解したものについては、交流インピーダンス法により室温でのイオン伝導度と粘度を評価した。結果を(表2)に示す。
前記(実施例1)、(実施例2)で使用したサンプル7のBMI・CF3SO3の非水電解液を用いて、非水有機溶剤との混合溶媒を検討した。非水有機溶剤として、プロピレンカーボネート(PC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(DMC)をそれぞれ0、10、20、50、70体積%混合し、溶解度(肉眼で評価)、イオン伝導度、溶液粘度の評価、測定を行った。Al塩の濃度はすべて1.0Mとした。その結果を表3に示す。
前記(実施例3)で作製したBMI・CF3SO3:PC=90:10、Al塩1Mの非水電解液を利用してアルミニウム濃淡電池を作製した。アルミニウム板を負極1、白金板を正極3として、非水電解液2に電極を浸し、放電電位の測定を行った。作製したアルミニウム濃淡電池の概略図を図1に示す。
<実施例1>
正極活物質としてAl2(MoO4)3を用いたコインセルを作製した(図2)。正極活物質となるAl2(MoO4)3は、Al(OH)3とMoO3をモル比2:3で十分混合粉砕し、850℃×4時間で焼成を行い、ライカイキにて十分粉砕した後、粉末X線回折測定により結晶系が単一な菱面体晶であることを確認して正極活物質とした。
<実施例2>
正極活物質をAl0.5Sc0.5(MoO4)3として、コインセルを作製した。
<比較例1>
正極活物質に炭素粉末を用いて、<実施例1><実施例2>と同様にコインセルを作製した。
<比較例2>
正極活物質をAlV3O9として、<実施例1><実施例2>と同様にしてコインセルを作製した。
<比較例3>
正極活物質としてFeS2を用いた以外は<実施例1><実施例2>と同様にコインセルを作製した。
<実施例3>
<実施例3>として、正極活物質に(AlxSc1−x)2(WO4)3を用いたコインセルを作製した。
<実施例4>
表6に示す正極活物質、電解液を用いてコインセルを作製した。負極、セパレータ等は<実施例1>と同様とした。
2: 非水電解液
3: 正極
4: 負極リード
5: 正極リード
21:負極ケース
22:負極
23:電解液
24:セパレータ
25:ガスケット
26:正極
27:正極ケース
Claims (7)
- アルキル基が炭素数1〜6のアルキル基である、請求項1に記載の非水電解液。
- さらに非水有機溶媒を含む、請求項1に記載の非水電解液。
- 前記非水有機溶媒が、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネートから選択される少なくとも1種を含む、請求項3に記載の非水電解液。
- 負極、非水電解液及び正極を含む二次電池であって、前記非水電解液が請求項1に記載の非水電解液である二次電池。
- 前記負極における活物質がアルミニウム及びアルミニウム合金の少なくとも1種である、請求項5に記載の二次電池。
- 前記正極における活物質が、下記一般式(3)
(AlxM1−x)2(M’O4)3 (3)
(但し、MはM2 aM3 bM4 cであって、M2はMg、Ca、Sr及びBaから選択される2価の金属元素の少なくとも1種、M3はSc、Y、Ga及びInから選択される3価の金属元素の少なくとも1種、M4はZr及びHfから選択される4価の金属元素の少なくとも1種を示す。M’はW又はMoを含む6価の金属元素を示す。0≦a<1、0≦b<1、c=a、0<x≦1、(2a/(1−x))+(3b/(1−x))+(4c/(1−x))=3)
で示される酸化物である、請求項5に記載の二次電池。
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