WO2006115023A1 - 非水電解液、およびそれを用いた電気化学エネルギー蓄積デバイス並びに非水電解液二次電池 - Google Patents
非水電解液、およびそれを用いた電気化学エネルギー蓄積デバイス並びに非水電解液二次電池 Download PDFInfo
- Publication number
- WO2006115023A1 WO2006115023A1 PCT/JP2006/307538 JP2006307538W WO2006115023A1 WO 2006115023 A1 WO2006115023 A1 WO 2006115023A1 JP 2006307538 W JP2006307538 W JP 2006307538W WO 2006115023 A1 WO2006115023 A1 WO 2006115023A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- aqueous electrolyte
- aqueous
- group
- electrolytic solution
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 147
- 238000012983 electrochemical energy storage Methods 0.000 title claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 150000003949 imides Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 54
- 239000008151 electrolyte solution Substances 0.000 claims description 45
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 41
- 229910013075 LiBF Inorganic materials 0.000 claims description 31
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 25
- 159000000002 lithium salts Chemical class 0.000 claims description 25
- -1 carbonate compound Chemical class 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 229910013872 LiPF Inorganic materials 0.000 claims description 7
- 101150058243 Lipf gene Proteins 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 3
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005151 nonafluorobutanesulfonyl group Chemical group FC(C(C(S(=O)(=O)*)(F)F)(F)F)(C(F)(F)F)F 0.000 claims description 2
- KURIPTHAZOPONO-UHFFFAOYSA-N 1,1,1-trifluoro-2-[2-(2,2,2-trifluoroethoxy)ethoxy]ethane Chemical compound FC(F)(F)COCCOCC(F)(F)F KURIPTHAZOPONO-UHFFFAOYSA-N 0.000 claims 1
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 claims 1
- KWTBOFRRIKHCQZ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li].C1CCCCC1 KWTBOFRRIKHCQZ-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 56
- 229910001416 lithium ion Inorganic materials 0.000 description 56
- 239000010410 layer Substances 0.000 description 34
- 150000002500 ions Chemical class 0.000 description 33
- 239000003125 aqueous solvent Substances 0.000 description 30
- 239000003990 capacitor Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910021383 artificial graphite Inorganic materials 0.000 description 13
- 239000011888 foil Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 239000007770 graphite material Substances 0.000 description 7
- 238000003780 insertion Methods 0.000 description 7
- 230000037431 insertion Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- BCKARVLFIJPHQU-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole-4-carboxylic acid ethyl ester Chemical compound CCOC(=O)C=1C(C)=NNC=1C BCKARVLFIJPHQU-UHFFFAOYSA-N 0.000 description 4
- 229910013188 LiBOB Inorganic materials 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- ZKNHDJMXIUOHLX-UHFFFAOYSA-N 2-ethoxy-1,1,1-trifluoroethane Chemical compound CCOCC(F)(F)F ZKNHDJMXIUOHLX-UHFFFAOYSA-N 0.000 description 1
- DQHCJQDPISNGEP-UHFFFAOYSA-N 4,5-bis(ethenyl)-1,3-dioxolan-2-one Chemical compound C=CC1OC(=O)OC1C=C DQHCJQDPISNGEP-UHFFFAOYSA-N 0.000 description 1
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010701 LiFeP Inorganic materials 0.000 description 1
- 229910012097 LiSbF Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- DFVFSEZEOFMQIF-UHFFFAOYSA-N O.O.O.O.O.O.[Li] Chemical compound O.O.O.O.O.O.[Li] DFVFSEZEOFMQIF-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000005002 aryl methyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- NTIFKWPEJRPCOU-UHFFFAOYSA-N carbonic acid;hex-1-ene Chemical compound OC(O)=O.CCCCC=C NTIFKWPEJRPCOU-UHFFFAOYSA-N 0.000 description 1
- OFXDKOYPVIXNTE-UHFFFAOYSA-N carbonic acid;stilbene Chemical compound OC(O)=O.C=1C=CC=CC=1C=CC1=CC=CC=C1 OFXDKOYPVIXNTE-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- BPFOYPDHLJUICH-UHFFFAOYSA-N ethenyl ethyl carbonate Chemical compound CCOC(=O)OC=C BPFOYPDHLJUICH-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- IEYPVFIAXMWHSZ-UHFFFAOYSA-N lithium nickel(2+) trinitrate Chemical compound [Li+].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IEYPVFIAXMWHSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
Classifications
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- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- 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
- H01M2300/0025—Organic electrolyte
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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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- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a non-aqueous electrolyte used for an electric double layer capacitor, a secondary battery, etc., and an electrochemical energy storage device and a non-aqueous electrolyte secondary battery using the same.
- An electric double layer capacitor in which polarizable electrodes are used for a positive electrode and a negative electrode accumulates electrochemical energy by adsorption of cations and anions in a non-aqueous electrolyte solution to the electrode surface during charging. For this reason, since the ion concentration in the non-aqueous electrolyte decreases in the charging process, the resistance inside the electric double layer capacitor increases. In addition, when the low ion concentration non-aqueous electrolyte is used, the number of ions that can be adsorbed decreases, so the electric capacity stored in the electric double layer capacitor decreases. Therefore, in order to increase the energy density of the electric double layer capacitor, it is necessary to increase the ion concentration in the non-aqueous electrolyte.
- lithium ions pass through the non-aqueous electrolyte and move between the positive electrode and the negative electrode.
- the ion concentration in the non-aqueous electrolyte does not change during discharge in the primary battery and during charging and discharging in the secondary battery. Therefore, in order to increase the energy density of the non-aqueous electrolyte battery, it is conceivable to increase the amounts of the positive electrode active material and the negative electrode active material and reduce the amount of non-aqueous electrolyte solution. Then, while it is necessary to maintain the amount of ions that can move between the positive and negative electrodes while reducing the amount of non-aqueous electrolyte, it is necessary to increase the ion concentration in the non-aqueous electrolyte.
- the electric double layer capacitor as described above is used in non-aqueous electrolyte batteries, and is used in non-aqueous electrolytes.
- Typical non-aqueous solvents to be used are cyclic carbonate ethylene carbonate (hereinafter abbreviated as EC), propylene carbonate (hereinafter abbreviated as PC), butylene carbonate (hereinafter abbreviated as BC), and cyclic ester.
- Nonaqueous electrolytes contain lithium hexafluorophosphate (LiPF) in these nonaqueous solvents.
- LiBF Lithium tetrafluorinated
- LiCIO lithium parked lithium
- LiTFSI lithium salt such as [trifluoromethanesulfonyl] imide
- concentration of the lithium salt dissolved in the non-aqueous electrolyte is usually only about 0.8 mol / kg.
- the molar ratio is 1: 4 (2.2 mono-liter / kg).
- the concentration mixed with is the limit in terms of solubility.
- 1, 2-dialkoxyethane as a non-aqueous solvent, such as 1, 2-dimethoxyethane (hereinafter abbreviated as DME).
- DME 1, 2-dimethoxyethane
- Patent Document 1 LiBF and DME
- Liquid, and (DME + EME) / LiBF molar ratio is (0.5 + 0.5) / 1 non-aqueous electrolyte at normal temperature
- LiBF or more is used as a lithium salt.
- LiPF lithium trifluoromethanesulfonate
- LiCF 2 SO 4 lithium trifluoromethanesulfonate
- LiSbF 2 lithium hexafluoroarsenate
- LiAsF 2 lithium hexafluoroarsenate
- non-aqueous electrolyte solidifies at room temperature, its use as a non-aqueous electrolyte for electrochemical energy storage devices is difficult.
- a non-aqueous electrolyte secondary battery in which a graphite material that absorbs and releases lithium ions is used as a negative electrode active material, DME or a kind of 1,2-dialkoxypetane is used.
- DME graphite material that absorbs and releases lithium ions
- 1,2-dialkoxypetane is used.
- the mixed solvent when used as a non-aqueous solvent of the electrolyte, it contains about 1 M of LiCIO.
- Non-patent Document 1 It has been conventionally confirmed that lithium ions can not be inserted into the graphite layer even in a non-aqueous electrolyte having a low ion concentration (Non-patent Document 1). This is considered to be because DME decomposes on graphite. For this reason, electrochemical insertion of lithium ions into the graphite material does not occur in the non-aqueous electrolyte containing DME, and therefore non-aqueous electrolytes for non-aqueous electrolyte secondary batteries using the graphite material as the negative electrode active material. It has been considered that 1, 2-dialkoxy ethane such as DME can not be used as an electrolyte. On the other hand, in the non-aqueous electrolyte secondary battery provided with the negative electrode of the present invention, which has the ability to use a graphite material, the high ion concentration of EME / LiBF is 1/1.
- Patent Document 1 Japanese Patent Application Laid-Open No. 11-107468
- Patent Document 2 Japanese Patent Application Laid-Open No. 3-84871
- Non-Patent Document 1 ⁇ ⁇ "," High-density Lithium Secondary Battery “, 1st Edition, Technosystem Co., Ltd., March 14, 1998, pl84-185
- the present invention has been made in view of the above-described problems, and provides a high stability non-aqueous electrolyte having high ion concentration, and thus an electrochemical energy storage device of high energy density, and a non-aqueous electrolyte.
- An object of the present invention is to provide an electrolyte secondary battery.
- One aspect of the present invention is that (A) Formula R—O—CH 2 —CH—O—R (where R and R ′ are the same. Each of which is an unsubstituted or fluorine-substituted alkyl group having 3 or less carbon atoms) and (B) lithium bis [trifluoromethanesulfonyl] imide (LiTFSI) And a molar ratio [(A) / (B)] of not less than 0.75 and not more than 2, and which is a liquid at normal temperature.
- FIG. 1 is a view showing charge characteristics of a graphite negative electrode in each non-aqueous electrolytic solution of Example 3 and Comparative Example 2 of the present invention.
- the non-aqueous electrolyte solution of the present invention is represented by the formula (A):
- lithium bis [trifluoromethanesulfonyl] imide which is represented by (1) or (2) which is an unsubstituted or fluorine-substituted alkyl group having 3 or less carbon atoms
- LiTFSI lithium bis [trifluoromethanesulfonyl] imide
- the non-aqueous electrolyte of the present invention maintains a liquid state even at high ion concentration at normal temperature, and is stable even at a high temperature of 60 ° C.
- TFSI ion bis [trifluoromethanesulfonyl] imide ion
- the BF ion contained in the non-aqueous electrolytic solution is a small amount of impurities having active hydrogen such as water.
- the non-aqueous electrolyte When present in the non-aqueous electrolyte, they react to generate hydrogen fluoride (HF).
- HF hydrogen fluoride
- the generated HF decomposes 1, 2-dialkoxy ketane, causing discoloration of the electrolytic solution, and the decomposition is remarkable, and in this case, the decomposition product reacts with the electrode.
- This decomposition will degrade the capacity and other properties of the electrochemical energy storage device.
- TFSI ion is less likely to generate HF even in non-aqueous electrolytes in which impurities having active hydrogen such as water are present. Therefore, the non-aqueous electrolyte containing the TFSI ion of the present invention is approximately in the middle. In order to maintain the acidity of the reaction, it is considered that the decomposition of the 1, 2_ dialkoxy ketone is suppressed, and a stable non-aqueous electrolyte can be obtained.
- a non-aqueous electrolyte battery provided with a negative electrode containing graphite as a negative electrode active material
- a non-aqueous electrolyte battery using 1,2-dialkoxyethane as a non-aqueous solvent and containing only LiBF as a lithium salt in a non-aqueous electrolyte battery provided with a negative electrode containing graphite as a negative electrode active material
- a non-aqueous electrolyte battery using 1,2-dialkoxyethane as a non-aqueous solvent and containing only LiBF as a lithium salt 1,2-dialkoxyethane
- the graphite structure is destroyed regardless of the ion concentration, but in the case of a non-aqueous electrolyte containing LiTFSI as a lithium salt, the 1,2 dialkoxyethane of the present invention is used as a non-aqueous solvent. It was found that lithium ion occluding and releasing between the graphite layers occurred more smoothly at the ion concentration. The reason for this is not necessarily clear, but the non-aqueous electrolyte in which LiTFSI is dissolved at a high concentration is solvated to react with graphite, and the amount of free, free, 1,2-dialkoxyether is It is speculated to reduce the
- the content ratio of 1,2-dialkoxypetane to be added and (B) lithium bis [trifluoromethanesulfonyl] imide is 0.75 or more and 2 or less in the molar ratio of [(A) / (B)]. .
- this is a non-aqueous electrolyte in which the LiTFSI of the present invention and 1, 2-dialkoxyketane are combined, and when the molar ratio of (A) / (B) is 2 or less, to lithium ion graphite
- the reasons for the stable introduction of H. can be considered as follows. That is, by using a high concentration non-aqueous electrolyte in which the molar ratio of (A) Z (B) is 2 or less, TFSI ions, rather than 1,2-dialkoxypetane, are preferentially reduced on the graphite. It becomes disassembled.
- examples of the 1,2-dialkoxypetane used in the present invention include the following.
- EME Ethoxy _2-Methoxyetan
- MTFEE 1-Methoxy _ 2_ trifluoroethoxyethane
- DEE 1, 2-Diethoxyethane
- ETFEE 1-Ethoxy-1-trifluoroethoxyetane
- BTFEE 2-Bis [trifluorofluoro] ethane
- DPE 2-Dipropoxetane
- 1, 2-dialkoxyketones may be used alone or in combination of two or more.
- DEE it is preferable to use DEE as a 1,2-dialkoxyketane because it becomes a liquid at normal temperature in a wide range of compositions and a non-aqueous electrolyte having a high ion concentration can be obtained.
- DEE it is preferable to use DEE in combination, when 1,2 dialcoquitane in which R and R 'are an unsubstituted alkyl group such as DME or EME is used as a non-aqueous solvent.
- the content ratio of DEE to 1,2-dialkoxyethane having an unsubstituted alkyl group other than DEE has a molar ratio [1, 2-dianolecoxitane having an unsubstituted alkyl group other than DEE. / DEE], 1 or less is preferable.
- the carbon number of R and R ′ of 1, 2-dialkoxyketane represented by the formula R — — CH — CH—0—R ′ is 3 or less, preferably 2 or less.
- R and R ′ are preferably one group selected from the group consisting of CH group, CH group, CF group, and CH CF group, since an electrolyte having a higher concentration can be obtained as the molecular weight of the non-aqueous solvent decreases. Re ,.
- a 1,2-dialkoxyacetan in which at least one of R and R ′ is a CH CF group for example, MTFEE, ETF having a CH CF group at the end
- EE and BTFEE are due to the electron withdrawing effect of fluorine in the fluorine-substituted alkyl group. It is preferable because the oxidation resistance potential is increased and a high charging voltage can be used. Since non-aqueous electrolytes containing these 1,2-substituted alkoxy groups having a fluorine-substituted alkyl group tend to have reduced reduction resistance, R and R ′ each represent an unsubstituted alkyl group. It is preferable to use 1, 2- dialkoxykete in combination. At least one selected from DME, DEE, and EME is preferred as the 1,2-dialkoxy ketone having such an unsubstituted alkyl group.
- the mixing ratio of the 1,2-dialkoxytane having at least one fluorine-substituted alkyl group to the 1,2-dialkoxyketane having an unsubstituted alkyl group has a molar ratio [having a fluorine-substituted alkyl group: 1,2 —Dialkoxyketane / 1,2-dialkoxyketane having an unsubstituted alkyl group], preferably at least 0 ⁇ 1, at most 1.
- a cyclic carbonate such as EC may be added as a non-aqueous solvent to a single or a mixture of the above-mentioned 1, 2-dialkoxyketanes.
- the addition ratio of these other non-aqueous solvents is preferably such that the molar ratio is preferably less than the total molar amount of 1, 2 -dialcoxitane in the non-aqueous electrolyte [carbonate compound / 1, 2-di alkoxy]], ⁇ ⁇ 05 or more, 0.1 or less is more preferable.
- VC vinylene carbonate
- Vec butyl ethylene carbonate
- DVec divinylethylene carbonate
- Pec phenyl ethylene carbonate
- DPec diphenyl ethylene carbonate
- Vec and Pec are preferable.
- MVC methyl boule carbonate
- EVC ethyl vinyl carbonate
- DVC dibule carbonate
- AM C aryl methyl carbonate
- AEC arylethyl carbonate
- DAC diallyl carbonate
- Examples include APC and abbreviations, and diflic acid phosphonates (hereinafter referred to as DPC) and the like, with DAC, APC and DPC being particularly preferable.
- the non-aqueous electrolytic solution of the present invention is a solution containing lithium bis [trifluoromethanesulfonyl] imide (LiTFSI) as a lithium salt, and further LiPF, LiBF, LiCIO, lithium bis [pentafluoroethan sulfonyl] imide (
- LiBETI lithium [trifluoromethane sulfonyl] [nonafluorobutane sulfonyl] imide
- LiMBSI lithium cyclohexafluoropropanone 1,3-bis [sulfonyl] imide
- LiCHSI lithium bis [oxalate (2_)] borate
- LiBOB lithium trifluoromethyl trifluoride
- LiCF 6 lithium pentafluorotriflate
- lithium salts such as F]
- LiPF LiPF
- LiBF LiBF
- LiBETI LiPF
- the combined use of at least one lithium salt selected from the group consisting of MBSI, LiCHSI, LiBOB, LiCFBF and LiCFBF is preferred.
- the mixing ratio of the lithium salt is suitably determined such that the non-aqueous electrolyte is stably present as a liquid at normal temperature, and preferably 0.10 or more and 0.2 or less in molar ratio of the other lithium salt to LiTFSI. .
- a non-aqueous electrolyte containing only LiTFSI as a lithium salt tends to corrode the aluminum of the positive electrode current collector.
- they are used in combination to form a passive film and to suppress corrosion.
- the electrochemical energy storage device of the present invention comprises a positive electrode, a negative electrode, and the non-aqueous electrolyte described above. Since the non-aqueous electrolyte solution of the present invention is stably present as a liquid even at high ion concentration as described above, it is used in electrochemical energy storage devices such as electric double layer capacitors and non-aqueous electrolyte batteries. Will yield high energy density electrochemical energy storage devices.
- the non-aqueous electrolytic solution of the present invention is suitably used for a non-aqueous electrolytic solution secondary battery provided with a negative electrode having graphite as a negative electrode active material.
- a non-aqueous electrolytic solution secondary battery provided with a negative electrode having graphite as a negative electrode active material.
- Graphite used as the negative electrode active material of the non-aqueous electrolyte secondary battery of the present invention includes, in addition to natural graphite and artificial graphite, a highly crystalline carbon material close to graphite, such as mesophase pitch graphite Fibers, graphitized mesocarbon microbeads, vapor grown carbon fibers, graphite whiskers and the like can be used, and among these, graphite having a crystal structure with an interlayer distance of about 3.5 A or less at which high energy density can be expected is preferable.
- the negative electrode of the non-aqueous electrolyte secondary battery is prepared by using a solvent such as N_methyl_2_ pyrrolidone (NMP) as described above, a negative electrode active material, a binder, and a thickener and, if necessary, a conductive agent.
- NMP N_methyl_2_ pyrrolidone
- the paste prepared by mixing and mixing is applied, for example, on a copper current collector to a predetermined thickness, dried, rolled, and cut.
- a conventionally known material is used as a constituent material used for the positive electrode of the non-aqueous electrolyte secondary battery of the present invention.
- composite oxides such as lithium cobaltate, lithium nickel nitrate, lithium manganate, lithium iron phosphate and the like are used as the positive electrode active material.
- the positive electrode of the non-aqueous electrolyte secondary battery is prepared by mixing a positive electrode active material as described above, a binder, and, if necessary, a thickener and a conductive agent, using a solvent such as NMP. For example, it is manufactured by applying an aluminum current collector so as to have a predetermined thickness, drying, rolling and cutting.
- the non-aqueous electrolyte secondary battery of the present invention has an electrode assembly having a structure in which the electrode is wound or stacked after the positive electrode and the negative electrode produced as described above are disposed opposite to each other with the separator interposed therebetween.
- the electrode body and the non-aqueous electrolytic solution are inserted into a battery can and manufactured through a sealing step.
- Example 1 The effect of lithium salt species on the high temperature stability of non-aqueous electrolyte was investigated. DME, DEE and LiTFSI were mixed at a molar ratio of (DME + DEE) / LiTFSI at (0.5 + 0.5) / 1 to prepare a non-aqueous electrolyte. The obtained liquid was transparent at normal temperature.
- the prepared non-aqueous electrolytic solution is placed in a container made of tetrafluoroethylene 'perfluoroalkyl methacrylate copolymer resin (hereinafter abbreviated as PFA), sealed, A container was stored in an aluminum laminate bag and sealed. After the container was stored at 60 ° C. for 10 days, the change in color tone of the non-aqueous electrolyte was examined. As a result, the non-aqueous electrolyte of Example 1 was maintained in a transparent state.
- PFA tetrafluoroethylene 'perfluoroalkyl methacrylate copolymer resin
- a solution was prepared.
- the obtained liquid was transparent at normal temperature.
- the prepared non-aqueous electrolyte is
- Example 1 In the same manner as in Example 1, the container was placed in a PFA container and sealed, and the PFA container was placed in an aluminum laminate bag and sealed. After the container was stored at 60 ° C. for 10 days, the change in color tone of the non-aqueous electrolyte was examined. As a result, the non-aqueous electrolyte of Comparative Example 1 was discolored to deep orange.
- Table 1 shows the results of these evaluations.
- non-aqueous solvent of Example 1 a mixed solvent of DME and DEE was used, and the non-aqueous solvent of Comparative Example 1 was used.
- Water solvent is the power used by EME's sole solvent. This is because the above-mentioned high ion concentration, LiT FSI, has not found a common solvent composition capable of dissolving LiBF.
- Table 2 shows the composition of the non-aqueous electrolyte which is liquid at normal temperature. Each prepared non-aqueous electrolyte was stored at 60 ° C. for 10 days in the same manner as in Example 1, and the change in color tone after storage was examined.
- the non-aqueous electrolytic solution of the present invention containing 1, 2-dialkoxyethane as a non-aqueous solvent and LiTFS I as a lithium salt is a total of 1, 2- dialkoxy to LiTFSI. Even in the high concentration range where the molar ratio of ethanol is 0.72, it can be seen that the non-aqueous electrolyte is a stable non-aqueous electrolyte which is liquid at normal temperature and shows no change in color tone.
- the composition has a DEE / LiTFSI molar ratio of 0.5 / 1. In the case, all LiTFSI could not be dissolved.
- non-aqueous electrolytes in which only DME or EME was used as 1,2-dialkoxyketane tended to become solid at normal temperature, but the molar ratio of DEE as non-aqueous solvent was 0.5
- the non-aqueous electrolytic solution in which the mixed solvent of the above (the molar ratio of [DME or EMEZ DEE] is 1 or less) was a liquid. Therefore, in order to obtain an electrolytic solution which is liquid at normal temperature, it is preferable to use DEE in combination when only 1,2-dialkoxyketane having unsubstituted R and R 'is contained as a non-aqueous solvent.
- the solubility of LiTFSI tends to decrease in a non-aqueous electrolyte solution in which only a 1,2-dialkoxypetane having a terminal alkyl group of 3 or more, such as DPE, is used as a non-aqueous solvent.
- a 1,2-dialkoxypetane having a terminal alkyl group of 3 or more, such as DPE is used as a non-aqueous solvent.
- the number of carbon atoms of the terminal alkyl group is 2, 2 or less. Use is preferred.
- An artificial graphite powder (MAG-D, manufactured by Hitachi Chemical Co., Ltd.) was used as a negative electrode active material that occludes and releases lithium ions by charge and discharge.
- the negative electrode plate was produced as follows. First, 75 parts by mass of artificial graphite powder, 20 parts by mass of acetylene black as a conductive agent, 5 parts by mass of polyvinylidene vinylidene resin as a binder, and dehydrated N-methyl_2_ pyrrolidone as a dispersion solvent are mixed. The Next, this mixture was applied to one side of a 20 zm thick copper foil current collector and dried to form an 80 z m thick active material layer. Then, the copper foil current collector on which the active material layer is formed is cut out to a size of 35 mm ⁇ 35 mm, and a 0.5 mm-thick copper current collector plate with a lead attached to the obtained copper foil current collector is ultrasonically welded. The negative electrode plate was manufactured.
- the molar ratio of DME, DEE, LiTFSI, and force (DME + DEE) ZLiTFSI was mixed so as to be (0.5 + 0.5) / 1 to prepare a non-aqueous electrolyte.
- FIG. 1 is a diagram showing a change in potential when a force Sword electric quantity of 60 mAh / g is applied to artificial graphite powder.
- the potential after the completion of energization in the non-aqueous electrolyte of this example is about 0.2 V, and this potential indicates that lithium ions intrude into the graphite layer to form a third stage structure. It shows. That is, it is understood that lithium ions can be stably incorporated in a non-aqueous electrolytic solution containing 1,2-dialkoxyethane as a non-aqueous solvent and LiTFSI as a lithium salt at a high concentration.
- Example 3 In the same manner as in Example 3, a negative electrode plate made of artificial graphite powder was produced.
- the negative electrode plate manufactured as described above is used as a test electrode, and a lithium metal foil is used as a counter electrode and a reference electrode, and the lithium ion is electrolyzed into artificial graphite powder in a prepared non-aqueous electrolyte. Insertion was attempted. Insertion conditions were set to 20 ° C. and 0.03 mA / cm 2 .
- FIG. 1 is a diagram showing a potential change when a force of 60 mAh / g force electric charge is applied to artificial graphite powder.
- the potential after the end of energization in the non-aqueous electrolyte of this comparative example has not dropped to the potential indicating the formation of the third stage structure. That is, it is shown that lithium ion insertion did not occur. It is speculated that this is because lithium ion solvated in EME, which is not lithium ion alone, intercalates between the graphite layers and breaks the layered structure of the graphite.
- the non-aqueous electrolytic solution of the present invention containing 1, 2-dialkoxyethane as the non-aqueous solvent and LiTFSI at a high ion concentration has a negative electrode made of a graphite material that absorbs and releases lithium ions. It can be applied to non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries.
- the lithium ion battery having the non-aqueous electrolyte of the present invention was assembled, and the battery characteristics were evaluated as follows.
- LiFePO was used as a positive electrode active material that absorbs and releases lithium ions by charge and discharge.
- the positive electrode plate was produced as follows. First, LiFeP
- a vinylidene fluoride resin was mixed, and this mixture was dispersed in dehydrated N_methyl_2-pyrrolidone to prepare a slurry-like positive electrode mixture.
- the positive electrode mixture was applied onto a positive electrode current collector made of aluminum foil, dried, and rolled to form an active material layer.
- the aluminum foil current collector on which the active material layer was formed was cut into a size of 35 mm ⁇ 35 mm.
- a 0.5 mm thick aluminum current collector plate having a lead attached to the obtained aluminum foil current collector was ultrasonically welded to produce a positive electrode plate.
- Example 3 a negative electrode plate having an artificial graphite powder power was produced.
- the mixture was mixed to give (0.5 + 0.5) / 1 to prepare a non-aqueous electrolyte.
- the positive electrode plate and the negative electrode plate were arranged to face each other with a non-woven fabric made of polypropylene interposed therebetween, the positive electrode plate and the negative electrode plate were fixed with a tape and integrated to produce an electrode body.
- this electrode body was housed in a cylindrical aluminum laminate bag having openings at both ends, and the openings on the lead portion side of both electrodes were welded. Then, the non-aqueous electrolytic solution prepared from the other opening was dropped.
- g represents per weight of LiFePO.
- a lithium ion battery was assembled in the same manner as in Example 4 except that a non-aqueous electrolytic solution was used in which the molar ratio of DME, LiTFSI, and DMEZLiTFSI was 2/1.
- a lithium ion battery was assembled in the same manner as in Example 4 except that a non-aqueous electrolytic solution was used in which the molar ratio of DME, LiTFSI, and DMEZLiTFSI was 3/1.
- the battery was charged and discharged under the conditions of upper limit voltage 4.0V and lower limit voltage 2.8V.
- the discharge capacity after 10 cycles was 65 mAh Zg.
- the reason why the discharge capacity of the battery of this comparative example was about half that of the discharge capacity of the battery of Example 4 was that DME was solvated between layers of the artificial graphite powder which is a negative electrode active material. It is because lithium ion was inserted and the graphite structure was destroyed.
- the ratio of 1,2-dialkoxyethane to LiTFSI which does not destroy the graphite structure is 2 or less in molar ratio of 1,2-dialkoxyketane / LiTFSI.
- a lithium ion battery was assembled in the same manner as in Example 4 except that the solution was used.
- the lithium ion battery power 20 ° C. assembled as described above It was charged and discharged under the conditions of upper limit voltage 4.0V and lower limit voltage 2.8V.
- the discharge capacity after 10 cycles was 17 mAh Zg.
- the reason why the discharge capacity of the battery of this comparative example was about 1/7 times the discharge capacity of the battery of Example 4 is that solvation was made between layers of artificial graphite powder which is a negative electrode active material. This is because the lithium ion is incorporated and the graphite structure is broken.
- a lithium ion battery was assembled in the same manner as Example 4, except that three types of non-aqueous electrolytes having the following respective compositions were used. The first is a non-aqueous electrolyte mixed with DEE, LiTFSI, and a power DEE / LiTFSI molar ratio of 1/1, and this non-aqueous electrolyte was used in lithium ion battery power.
- Battery of Example 6A I was told.
- the second is a non-aqueous electrolyte mixed with DEE / EC / LiTF SI / force at a molar ratio of DEE / EC / LiTFSI of 0.9 Z 0.1 / 1, and this non-aqueous electrolyte is used for lithium ion
- a battery was taken as the battery of Example 6B.
- the third is a non-aqueous electrolyte mixed with DEE / EC / LiTFSI / Vec / force at a molar ratio of 0.9 / 0.09 / 1 / 0.01, and this non-aqueous electrolyte is used.
- the lithium ion battery thus obtained was used as the battery of Example 6C.
- the cycle retention rate is 0.83 for the lithium ion battery of Example 6A, 0. 6 for Example 6B.
- Example 6C was 0.94. From the above results, it can be seen that the non-aqueous electrolytic solution of the present invention to which EC or Vec is added improves the cycle retention rate of the lithium ion battery.
- the characteristics of a lithium ion battery having a non-aqueous electrolyte comprising a non-aqueous solvent and a non-aqueous solvent containing LiTFSI and another lithium salt with LiTFSI are used as the non-aqueous solvent. It was investigated as follows.
- a lithium ion battery was assembled in the same manner as in Example 4 except that three types of non-aqueous electrolytes having the following compositions were used.
- the first is a mixture of DME, ETFEE, LiTFSI, and force (DME + ETFEE) at a molar ratio of (0.5 + 0.5) Zl at a molar ratio of ZLiTFSI, and a lithium ion battery using this non-aqueous electrolyte was used.
- the battery of Example 7A was used.
- the second is DME, ETFEE, LiTFSI, LiPF and force (DME + ETFEE) / LiTFSl / Li
- the lithium ion battery in which the electrolytic solution was used was regarded as the battery of Example 7B.
- the third one is DM Non-aqueous electrolyte mixed with (0.5 + 0.5) Z 0.99 / 0.01 in molar ratio of E, ETFEE, LiTFSI, LiBOB and force (DME + ETFEE) ZLiTFSl ZLiBBB, and this non-aqueous electrolyte is used.
- the lithium ion battery was regarded as the battery of Example 7C.
- the cycle maintenance rate is 0.77 for the lithium ion battery of Example 7A, 0. 6 for Example 7B.
- Example 7C was 0.88.
- the storage characteristics of the lithium primary battery having the non-aqueous electrolyte solution of the present invention were evaluated as follows.
- the lithium primary battery was assembled in the following procedure.
- a positive electrode active material ⁇ ⁇ ⁇ ⁇ ⁇ ( ⁇ phase and two phase coexist of three phases) were used. Then, in the same manner as in Example 4, the positive electrode
- a board was made.
- a lithium metal foil is used for the negative electrode plate, and after being cut into a size of 35 mm ⁇ 35 mm, a 0.5 mm-thick copper current collector plate with a lead attached thereto is crimped to the obtained lithium metal foil. It was done.
- the positive electrode plate and the negative electrode plate were disposed to face each other with the porous film made of polyethylene interposed therebetween, the positive electrode plate and the negative electrode plate were fixed with a tape and integrated to produce an electrode body.
- this electrode body was housed in a cylindrical aluminum laminate bag having openings at both ends, and the openings on the lead portion side of both electrodes were welded. Then, the non-aqueous electrolyte prepared from the other opening was dropped. [0089] After dropping, degassing was performed at 1300 Pa for 5 seconds. The opening on the injected side was sealed by welding to produce a lithium primary battery.
- the lithium primary battery assembled as described above was subjected to preliminary discharge under the conditions of 20 ° C. and 0.03 mA / cm 2 until the LiZMn molar ratio reached 0.05 Z1. After predischarge, the cells were stored at 60 ° C. for 1 month, and changes in internal impedance before and after storage were examined. As a result of measuring the resistance at 10 kHz, the resistance before storage was 2.3 ⁇ and the resistance after storage was 2.8 ⁇ .
- a lithium primary battery was assembled in the same manner as in Example 8 except that the solution was used.
- the electric double layer capacitor having the non-aqueous electrolyte of the present invention was evaluated as follows.
- the polarizable electrode was produced by the procedure shown below.
- the mass ratio of activated carbon powder made of phenol resin having a specific surface area of 1700 m 2 / g, acetylene black as a conductive agent, ammonium salt of carboxymethyl cellulose as a binder, and water and methanol as a dispersion solvent 10: 2 1: 1: 100: 40 were mixed to achieve a blending ratio.
- This mixture was applied and dried on one side of a 20 x m thick aluminum foil current collector, to form an 80 / m thick active material layer. And, the aluminum on which the active material layer is formed
- the 2 mm foil current collector was cut into a size of 35 mm ⁇ 35 mm.
- a 0.5 mm-thick aluminum current collector plate having a lead attached to the obtained aluminum foil current collector was ultrasonically welded to prepare a polarization electrode.
- An electrode made of artificial graphite powder produced in the same manner as in Example 3 as the negative electrode prepared as described above as the positive electrode was used. After a non-woven polypropylene separator made of polypropylene was placed between the two electrodes, a non-aqueous electrolyte was injected and the whole was placed in an aluminum laminate tube to produce an electric double layer capacitor.
- a non-aqueous electrolytic solution was used as the electrolytic solution, in which the molar ratio of DME, DEE, LiTFSI, and force (DME + DEE) / LiTFSI was (0.5 + 0.5) / 1.
- the assembled electric double layer capacitor was repeatedly charged and discharged in a voltage range of 2.0 to 3.8 V at a constant current of 0.3 mA / cm 2 at 20 ° C., and a change in capacitance was examined.
- the capacity retention ratio obtained by dividing the capacity after 1000 cycles by the capacity at 10th cycle was 0.96.
- An electric double layer capacitor was assembled in the same manner as in Example 9 except that the solution was used.
- the electric double layer capacitor assembled as described above was repeatedly charged and discharged in a voltage range of 2.0 to 3.8 V at a constant current of 0.3 mA / cm 2 at 20 ° C., after 54 cycles.
- the capacitance of the capacitor was almost zero. This is presumably because the potential of the positive electrode, which is a polarizable electrode, is overcharged and the EME is oxidized and decomposed because the potential of the negative electrode does not become negative during charging.
- one aspect of the present invention relates to (A) Formula R- 0-CH-CH _ _ _ R '
- R and R ′ may be the same or different and each is an unsubstituted or fluorine-substituted alkyl group having 3 or less carbon atoms, which is represented by the following formula (1): It is a non-aqueous electrolytic solution containing mubis [trifluoromethanesulfonyl] imide in a molar ratio of (0.75) to (2) or less [(A) / (B)] and being liquid at ordinary temperature. According to the above configuration, A high-temperature stable, high ion concentration non-aqueous electrolyte can be obtained which can provide an energy density electrochemical energy storage device.
- the above non-aqueous electrolyte has a carbon number of 2 or less in R and R '. According to the above configuration, since the concentration of LiTFSI can be set high, a non-aqueous electrolytic solution with high ion concentration can be obtained.
- R and R ′ each represent a CH group, a CH group, a CF group, or a CH
- One group selected from the group consisting of CF groups is preferred. According to the above configuration, since the low molecular weight 1,2-dialkoxy ketone is used as the non-aqueous solvent, the concentration of LiTFSI can be set high.
- non-aqueous electrolyte it is preferable that, as the 1,2-dialkoxypetane, at least one selected from the group force of MTFEE, ETFEE, and BTFEE be contained. According to the above configuration, a non-aqueous electrolytic solution which is liquid at normal temperature can be obtained as soon as a non-aqueous electrolytic solution having excellent oxidation resistance is obtained. can get.
- the present invention further relates to a non-aqueous electrolytic solution containing the above-described fluorine-substituted alkyl group-containing 1,2-dialkoxyethane as a non-aqueous solvent, further comprising DME, DEE, and EME. It is preferable to contain at least one selected from the group consisting of According to the above configuration, when the 1,2-dialkoxy ketone having a fluorine-substituted alkyl group is contained as the non-aqueous solvent, a non-aqueous electrolytic solution having a high ion concentration can be obtained.
- the present invention preferably further comprises a carbonate complex as a non-aqueous solvent in the above-described non-aqueous electrolyte. According to the above configuration, a non-aqueous electrolyte battery having excellent cycle characteristics can be obtained.
- the present invention is further directed to the above non-aqueous electrolytic solution further comprising, as a lithium salt, LiPF, LiBF, Li
- another aspect of the present invention is an electrochemical energy storage device comprising a positive electrode, a negative electrode, and the above non-aqueous electrolyte. Since the non-aqueous electrolyte of the present invention has high ion concentration and excellent stability, according to the above configuration, a high energy density electrochemical energy storage device can be obtained.
- Another aspect of the present invention is a non-aqueous electrolyte secondary battery including the positive electrode, a negative electrode having graphite as a negative electrode active material, and the above non-aqueous electrolyte.
- the non-aqueous electrolyte solution of the present invention lithium ions smoothly intercalate and deintercalate into the graphite layer without causing destruction of the graphite structure even at high ion concentration.
- a non-aqueous electrolytic solution secondary battery is obtained.
- the present invention it is possible to obtain a non-aqueous electrolytic solution which is excellent in stability and maintains a liquid state at normal temperature even at a high ion concentration. Therefore, the energy density of the electrochemical energy storage device can be increased by being used as an electrolytic solution of an electric double layer capacitor, a non-aqueous electrolytic cell and the like.
- lithium can be stably stored in a non-aqueous electrolytic solution containing 1,2-dialkoxyethane as a non-aqueous solvent. It can occlude and release ions, and can increase the energy density of lithium ion batteries.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2007514538A JPWO2006115023A1 (ja) | 2005-04-19 | 2006-04-10 | 非水電解液、およびそれを用いた電気化学エネルギー蓄積デバイス並びに非水電解液二次電池 |
EP06731485A EP1879252A4 (en) | 2005-04-19 | 2006-04-10 | WATER-FREE ELECTROLYTE SOLUTION, ELECTROCHEMICAL ENERGY STORAGE DEVICE THEREFOR AND SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE |
CN2006800132061A CN101164189B (zh) | 2005-04-19 | 2006-04-10 | 非水电解液、使用该非水电解液的电化学能量储存装置以及非水电解液二次电池 |
US11/918,869 US20090023074A1 (en) | 2005-04-19 | 2006-04-10 | Nonaqueous electrolyte solution, and electrochemical energy-storing device and nonaqueous-electrolyte- solution secondary battery using the same |
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JP2005120574 | 2005-04-19 | ||
JP2005-120574 | 2005-04-19 |
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PCT/JP2006/307538 WO2006115023A1 (ja) | 2005-04-19 | 2006-04-10 | 非水電解液、およびそれを用いた電気化学エネルギー蓄積デバイス並びに非水電解液二次電池 |
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US (1) | US20090023074A1 (ja) |
EP (1) | EP1879252A4 (ja) |
JP (1) | JPWO2006115023A1 (ja) |
KR (1) | KR20070121034A (ja) |
CN (1) | CN101164189B (ja) |
WO (1) | WO2006115023A1 (ja) |
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Also Published As
Publication number | Publication date |
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JPWO2006115023A1 (ja) | 2008-12-18 |
EP1879252A4 (en) | 2010-06-23 |
US20090023074A1 (en) | 2009-01-22 |
EP1879252A1 (en) | 2008-01-16 |
CN101164189A (zh) | 2008-04-16 |
CN101164189B (zh) | 2011-05-04 |
KR20070121034A (ko) | 2007-12-26 |
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