JPWO2014155992A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JPWO2014155992A1 JPWO2014155992A1 JP2015508009A JP2015508009A JPWO2014155992A1 JP WO2014155992 A1 JPWO2014155992 A1 JP WO2014155992A1 JP 2015508009 A JP2015508009 A JP 2015508009A JP 2015508009 A JP2015508009 A JP 2015508009A JP WO2014155992 A1 JPWO2014155992 A1 JP WO2014155992A1
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- Prior art keywords
- carbonate
- volume
- negative electrode
- positive electrode
- aqueous solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 53
- 150000005678 chain carbonates Chemical class 0.000 claims abstract description 49
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 41
- 239000007789 gas Substances 0.000 description 27
- 239000007773 negative electrode material Substances 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 15
- 239000012046 mixed solvent Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000011888 foil Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- -1 carbonate ester Chemical class 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000003115 supporting electrolyte Substances 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910011456 LiNi0.80Co0.15Al0.05O2 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910015014 LiNiCoAlO Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002388 carbon-based active material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002409 silicon-based active material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-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
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910017156 Ni0.80Co0.15Al0.05 Inorganic materials 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- AEHVMUMGWLAZNV-UHFFFAOYSA-N ethyl propan-2-yl carbonate Chemical compound CCOC(=O)OC(C)C AEHVMUMGWLAZNV-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 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 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000003466 welding Methods 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
- H01M10/056—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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
[正極活物質の作製]
正極材料としてLiNi0.80Co0.15Al0.05O2を準備した。まず、所定比率の硫酸ニッケルと硫酸コバルトを溶解した水溶液に、水酸化ナトリウムを含むアルカリ溶液を滴下して水酸化物の沈殿を得た。この水酸化物をNaAlO2水溶液中に分散させ、硫酸を用いて中和することにより水酸化アルミニウムを水酸化物の表面に均一に析出させた。その後、空気雰囲気中、700℃で10時間焼成し、3元系の酸化物である[Ni0.80Co0.15Al0.05]Oを得た。さらに、得られた酸化物に、Ni、Co、Alを合わせたモル数とLiのモル数との比が1:1になるように水酸化リチウム一水和物の粉末を混合し、酸素雰囲気中で750℃まで10時間で昇温し、750℃で熱処理を36時間行うことにより、目的とするLiNi0.80Co0.15Al0.05O2を得た。
上記のようにして得られた正極活物質(LiNi0.80Co0.15Al0.05O2)と、導電剤としてのアセチレンブラック粉末と、結着剤としてのポリフッ化ビニリデン(PVdF)とを、活物質と導電剤と結着剤との質量比が100:3:4の割合になるように混合した後、分散媒としてのN−メチル−2−ピロリドンを添加して混練し、正極スラリーを調製した。この正極スラリーを、正極集電体としてのアルミニウム箔(厚み15μm)の両面に塗布、乾燥し、アルミニウム箔上に正極活物質層を作製した後、圧延ローラにより圧延し、正極を作製した。得られた正極にはアルミニウム製の正極リードを取り付けた。
負極材料としてLi4Ti5O12を準備した。二酸化チタンと水酸化リチウムを混合したのち、空気中にて850℃で15時間加熱処理することにり、目的とするLi4Ti5O12を得た。
この負極活物質(Li4Ti5O12)と、導電剤としてのアセチレンブラック粉末と、結着剤としてのポリフッ化ビニリデン(PVdF)とを、活物質と導電剤と結着剤との質量比が100:3:4の割合になるように混合した後、分散媒としてのN−メチル−2−ピロリドンを添加して混練し、負極スラリーを調製した。この負極スラリーを、負極集電体としてのアルミニウム箔(厚み15μm)の両面に塗布、乾燥し、アルミニウム箔上に負極活物質層を作製した後、圧延ローラにより圧延し、負極を作製した。得られた負極にはアルミニウム製の負極リードを取り付けた。
プロピレンカーボネートを25体積%に固定し、(1)ジエチルカーボネート75体積%、(2)ジエチルカーボネート70体積%とジメチルカーボネート5体積%、(3)ジエチルカーボネート65体積%とジメチルカーボネート10体積%、(4)ジエチルカーボネート60体積%とジメチルカーボネート15体積%、(5)ジエチルカーボネート55体積%とジメチルカーボネート20体積%で混合した混合溶媒に対し、支持電解質塩としての六フッ化リン酸リチウム(LiPF6)を1.2mol/Lの濃度になるように溶解させて、非水電解質1〜5を調製した。
上記のように作製した正極、負極、正極と負極との間にセパレータを介在させて積層し、得られた積層物を捲回して、電極群を作製した。該電極群を外装体としてのアルミラミネートフィルム製容器に収容し、前述の非水電解質1〜5を、前記の電極群を収容したアルミラミネートフィルム製容器に注液した後、アルミラミネートフィルム製容器の開口部を加熱融着して密閉し、試験セル1〜5を作製した。正極リードおよび負極リードは前記加熱融着部分を通して、密閉性を保持した状態で容器外部に取り出した。
試験セル1〜5を20℃の恒温槽に収容し、以下のような定電流定電圧方式で充放電した。各試験セル1〜5を、電池電圧が2.8Vになるまで1Cレート(1Cとは1時間で全電池容量を使い切ることができる電流値)の定電流で充電した。電池電圧が2.8Vに達した後は、電流値が0.05Cになるまで、各試験セルを2.8Vの定電圧で充電した。次に、20分間休止した後、充電後の試験セルを、Cレートのハイレートの定電流で、電池電圧が1.5Vになるまで放電した。このような充放電を800サイクル繰り返した。1サイクル目の全放電容量に対するその後の各サイクルの全放電容量の割合(百分率値で求めた値)を算出し、これを放電容量維持率として図2にまとめた。放電容量維持率が低い程、サイクル特性が低下したと言える。
充放電前の試験セル1〜5の体積を測定した。そして、前述と同様の定電流定電圧方式で充放電を300サイクル繰り返し、300サイクル後の試験セル1〜5の体積を測定した。充放電前の試験セル1〜5の体積に対する300サイクル後の試験セル1〜5の体積の割合(百分率値で求めた値)を算出し、これをセル体積増加率として図3にまとめた。セル体積増加率が大きいほど、試験セル内部でのガス発生により電池が膨れたと言える。
(6)プロピレンカーボネートを25体積%、ジエチルカーボネートを75体積%、(7)プロピレンカーボネートを33体積%、ジエチルカーボネートを66体積%、(8)プロピレンカーボネートを40体積%、ジエチルカーボネートを60体積%、(9)プロピレンカーボネートを45体積%、ジエチルカーボネートを55体積%、(10)プロピレンカーボネートを50体積%、ジエチルカーボネートを50体積%、(11)プロピレンカーボネートを55体積%、ジエチルカーボネートを45体積%、(12)プロピレンカーボネートを60体積%、ジエチルカーボネートを40体積%、(13)プロピレンカーボネートを90体積%、ジエチルカーボネートを10体積%で混合した混合溶媒に対し、六フッ化リン酸リチウム(LiPF6)を1.2mol/Lの濃度になるように溶解させて、非水電解質6〜13を調製したこと以外は、実施例1と同様の試験セルを作製した。これらを試験セル6〜13とした。
試験セル1〜5を20℃の恒温槽に収容し、以下のような定電流定電圧方式で充放電した。各試験セル1〜5を、電池電圧が2.8Vになるまで1Cレート(1Cとは1時間で全電池容量を使い切ることができる電流値)の定電流で充電した。電池電圧が2.8Vに達した後は、電流値が0.05Cになるまで、各試験セルを2.8Vの定電圧で充電した。次に、20分間休止した後、充電後の試験セルを、1.0Cレートのハイレートの定電流で、電池電圧が1.5Vになるまで放電した。このような充放電を800サイクル繰り返した。1サイクル目の全放電容量に対するその後の各サイクルの全放電容量の割合(百分率値で求めた値)を算出し、これを放電容量維持率として図2にまとめた。放電容量維持率が低い程、サイクル特性が低下したと言える。
Claims (3)
- 正極と、チタン酸リチウムを含む負極と、前記正極と前記負極との間に介在するセパレータと、電解質塩及び非水溶媒を含む非水電解質と、を備える非水電解質二次電池であって、
前記非水溶媒は、プロピレンカーボネートと、一般式R1OCOOR2(R1及びR2は炭素数2以上のアルキル基)で表される鎖状カーボネートAと、一般式R3OCOOR4(R3はメチル基、R4はアルキル基)で表される鎖状カーボネートBとを含み、
前記非水溶媒中の前記プロピレンカーボネートの体積分率は25〜33体積%の範囲であり、前記非水溶媒中の前記鎖状カーボネートAの体積分率は65〜74体積%の範囲であり、前記非水溶媒中の前記鎖状カーボネートBの体積分率は1〜10体積%の範囲であることを特徴とする非水電解質二次電池。 - 前記鎖状カーボネートBは、ジメチルカーボネート、エチルメチルカーボネート、又はそれらの混合物から選択されることを特徴とする請求項1記載の非水電解質二次電池。
- 前記鎖状カーボネートAはジエチルカーボネートであることを特徴とする請求項1記載の非水電解質二次電池。
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JP2007294164A (ja) * | 2006-04-24 | 2007-11-08 | Gs Yuasa Corporation:Kk | 非水電解質二次電池 |
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