JP6904981B2 - リチウムイオン電池 - Google Patents
リチウムイオン電池 Download PDFInfo
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- JP6904981B2 JP6904981B2 JP2018564810A JP2018564810A JP6904981B2 JP 6904981 B2 JP6904981 B2 JP 6904981B2 JP 2018564810 A JP2018564810 A JP 2018564810A JP 2018564810 A JP2018564810 A JP 2018564810A JP 6904981 B2 JP6904981 B2 JP 6904981B2
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- phosphate
- positive electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 25
- -1 phosphoric acid ester compounds Chemical class 0.000 claims description 42
- 239000007774 positive electrode material Substances 0.000 claims description 35
- 239000011247 coating layer Substances 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 150000008282 halocarbons Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- LUVQJDCOCWBMEN-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl bis(prop-2-ynyl) phosphate Chemical compound P(=O)(OCC#C)(OCC#C)OC(C(F)(F)F)C(F)(F)F LUVQJDCOCWBMEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 claims description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 2
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- HPZCUDJYOUMWRW-UHFFFAOYSA-N bis(prop-2-ynyl) trifluoromethyl phosphate Chemical compound P(=O)(OCC#C)(OCC#C)OC(F)(F)F HPZCUDJYOUMWRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- GUICUMLKEBGGLD-UHFFFAOYSA-N ethyl bis(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC)OCC#C GUICUMLKEBGGLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- YFIBSNDOVCWPBL-UHFFFAOYSA-N hexa-1,5-diyne Chemical group C#CCCC#C YFIBSNDOVCWPBL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- HSAPVOPSUVJVGL-UHFFFAOYSA-N methyl bis(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OC)OCC#C HSAPVOPSUVJVGL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 2
- FCTINJHSYHFASK-UHFFFAOYSA-N tris(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC#C)OCC#C FCTINJHSYHFASK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- JRFGITQZJDGRPA-UHFFFAOYSA-L 3,3,3-trifluoropropyl phosphate Chemical compound [O-]P([O-])(=O)OCCC(F)(F)F JRFGITQZJDGRPA-UHFFFAOYSA-L 0.000 claims 1
- ASZGOLRLPYYUOA-UHFFFAOYSA-N 3-prop-2-ynylhex-5-ynyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCC(CC#C)CC#C ASZGOLRLPYYUOA-UHFFFAOYSA-N 0.000 claims 1
- 229910016569 AlF 3 Inorganic materials 0.000 claims 1
- 229910013716 LiNi Inorganic materials 0.000 claims 1
- OMQYESFLSJNBPZ-UHFFFAOYSA-N bis(prop-2-ynyl) 2,2,2-trifluoroethyl phosphate Chemical compound FC(F)(F)COP(=O)(OCC#C)OCC#C OMQYESFLSJNBPZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002222 fluorine compounds Chemical group 0.000 claims 1
- 238000007069 methylation reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910001512 metal fluoride Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- APCJFSLQFFTLSA-UHFFFAOYSA-N bis(prop-2-ynyl) 3,3,3-trifluoropropyl phosphate Chemical compound P(=O)(OCC#C)(OCC#C)OCCC(F)(F)F APCJFSLQFFTLSA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AIKFSRURHOARNU-UHFFFAOYSA-N propyl bis(prop-2-ynyl) phosphate Chemical compound CCCOP(=O)(OCC#C)OCC#C AIKFSRURHOARNU-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
電池ケースと、前記電池ケースの内部に配置された正極、負極及び非水電解液を含むリチウムイオン電池であり、前記正極は、正極活物質及び前記正極活物質の表面を被覆する被覆層を含み、前記正極活物質は、一般式1または一般式2に示された構成のうちの少なくとも1種を有する。
一般式1:LixNiyM1-yO2
ここで、0.5≦x≦1.2、0.5≦y≦1であり、Mは、Co、Mn、Al、Ti、Fe、Zn、Zr、及びCrからなる群から選ばれた少なくとも1種である。
一般式2:LikCozL1-zO2
ここで、0.5≦k≦1.2、0.5<z≦1であり、Lは、Ni、Mn、Al、Ti、Fe、Zn、Zr、及びCrからなる群より選ばれた少なくとも1種である。
前記被覆層は金属酸化物及び/又はフッ化物である。
前記負極は、負極活物質を含み、前記負極活物質は、黒鉛またはケイ素含有炭素材料から選ばれた少なくとも1種である。
前記非水電解液は、構造式1に示された不飽和リン酸エステル化合物のうちの少なくとも1種を含む。
構造式1:
上記一般式1において、0.8≦x≦1.1であることが好ましい、例えばxは0.8、0.9、1.0又は1.1であってよく、一般式1において、0.8≦y≦1、例えばxは0.8、0.9又は1.0であってよい。
一般式1に示された化合物または一般式2に示された化合物と、Zn、Mg、Al、Zr、Cr、Ti、Ag、Nb、Y、Sr、W、Mo、Pb、Cd、Ca、Ba及びSnからなる群より選ばれた少なくとも一種の金属元素を含む水溶液とを均一に混合して、得られた混合物を熱処理して、式1に示された化合物または式2に示された化合物を表面被覆する。
本実施例に係るリチウムイオン電池の製造方法は、正極を製造するステップ、負極を製造するステップ、電解液を調製するステップ、隔膜を製造するステップ及び電池を組み立てるステップを備える。詳細は次の通りである。
実施例2−25において、被覆層と不飽和リン酸エステル化合物の具体的な化合物及びその使用量以外は、実施例1と同じとした。各実施例の具体的な化合物、及びその使用量は、表1、表3及び表5に示す通り、その使用量は、リチウムイオン電池の非水電解液の総重量に対する百分率に基づいて計算した。
(1)高温サイクル性能の試験45℃環境下において、製造した電池を1Cで4.35Vになるまで定電流定電圧充電して、次に1Cで3.0Vになるまで定電流放電した。充電/放電サイクルを500回繰り返した後に、第500回サイクルの容量維持率を計算し、高温サイクル性能を評価した。計算式は、次の通りとした。
500回サイクル後における容量維持率(%)=(第500サイクルの放電容量/第1サイクルの放電容量)×100%
電池容量維持率(%)=維持容量/初期容量×100%;
電池容量回復率(%)=回復容量/初期容量×100%;
電池厚み膨張率(%)=膨張厚み/初期電池厚み×100%。
25℃環境下において、製造した電池を1Cで4.35Vまで定電流定電圧充電した後、電流が0.01Cに低下するまで定電圧充電してから、1Cで3.0Vまで定電流放電して、常温放電容量を測定した。次いで、1Cで4.35Vまで定電流充電し、電流が0.01Cに低下するまで定電圧充電してから、−20℃の環境に12時間置いた後、0.2Cで3.0Vまで定電流放電し、−20℃の放電容量を測定した。
Claims (6)
- 充電終止電圧が4.3V以上であるリチウムイオン電池であり、
電池ケースと、電池ケース内部に配置された正極、負極及び非水電解液とを含み、
前記正極は、正極活物質及び前記正極活物質の表面を被覆する被覆層を含み、前記正極活物質は、一般式1または一般式2に示された構成のうちの少なくとも一種を有し、
一般式1:LixNiyM1-yO2
式中、0.5≦x≦1.2、0.5≦y≦1であり、Mは、Co、Mn、Al、Ti、Fe、Zn、Zr、及びCrからなる群より選ばれた少なくとも1種であり、
一般式2:LikCozL1-zO2
式中、0.5≦k≦1.2、0.5<z≦1であり、Lは、Ni、Mn、Al、Ti、Fe、Zn、Zr、及びCrからなる群より選ばれた少なくとも1種であり、
前記被覆層の材質は、Zn、Mg、Al、Zr、Cr、Ti、Ag、Nb、Y、Sr、W、Mo、Pb、Cd、Ca、Ba及びSnのうちの少なくとも一種の酸化物及び/又はフッ化物であり、
前記正極活物質の表面を被覆する前記被覆層の含有量は、前記正極活物質と前記被覆層との総重量を基準として、0.5〜3%であり、
前記負極は、負極活物質を含み、前記負極活物質は、黒鉛またはケイ素含有炭素材料から選ばれた少なくとも1種であり、
前記非水電解液は、構造式1に示された不飽和リン酸エステル化合物のうちの少なくとも1種を含み、
構造式1:
前記非水電解液において、不飽和リン酸エステル系化合物の含有量は0.5〜2%であることを特徴とするリチウムイオン電池。 - 前記一般式1において、0.8≦x≦1.1;0.8≦y≦1であり、前記一般式2において、0.8≦z≦1であることを特徴とする請求項1に記載のリチウムイオン電池。
- 前記一般式1に示された正極活物質は、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.2O2、及びLiNi0.8Co0.15Al0.05O2からなる群より選ばれた一種であり、
一般式2に示された構成の正極活物質は、LiCoO2から選ばれたものであることを特徴とする請求項1に記載のリチウムイオン電池。 - 前記被覆層の材質は、ZnO、MgO、Al2O3、ZrO2、Cr2O3、AlF3、及びTiO2からなる群より選ばれた少なくとも一種であることを特徴とする請求項1に記載のリチウムイオン電池。
- 前記構造式1において、前記飽和炭化水素基は、メチル基、エチル基、プロピル基、イソプロピル基、及びブチル基からなる群より選ばれた一種であり、
前記不飽和炭化水素基は、ビニル基、アリル基、3−ブテニル基、イソブテニル基、4−ペンテニル基、アセテニル基、プロパルギル基、3−ブチニール基、及び1−メチル−2−プロピニル基からなる群より選ばれた一種であり、
前記ハロゲン化炭化水素基は、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、2,2,2−トリフルオロエチル基、2,2−ジフルオロエチル基、2,2,2−トリフルオロエチル基、3,3−ジフルオロプロピル基、3,3,3−トリフルオロプロピル基、及びヘキサフルオロイソプロピル基からなる群より選ばれた一種であることを特徴とする請求項1〜4のいずれか1項に記載のリチウムイオン電池。 - 前記不飽和リン酸エステル化合物は、トリプロパルギルホスフェート、ジプロパルギルメチルホスフェート、ジプロパルギルエチルホスフェート、ジプロパルギルプロピルホスフェート、ジプロパルギルトリフルオロメチルホスフェート、ジプロパルギル2,2,2−トリフルオロエチルホスフェート、ジプロパルギル3,3,3−トリフルオロプロピルホスフェート、ジプロパルギルヘキサフルオロイソプロピルホスフェート、トリアリルホスフェート、ジアリルメチルホスフェート、ジアリルエチルホスフェート、ジアリルプロピルホスフェート、ジアリルトリフルオロメチルホスフェート、ジアリル2,2,2−トリフルオロエチルホスフェート、ジアリル3,3,3−トリフルオロプロピルホスフェート、及びジアリルヘキサフルオロイソプロピルホスフェートからなる群より選ばれた一種または複数種であることを特徴とする請求項5に記載のリチウムイオン電池。
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