JP2015176672A - 非水電解液二次電池 - Google Patents
非水電解液二次電池 Download PDFInfo
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- JP2015176672A JP2015176672A JP2014050524A JP2014050524A JP2015176672A JP 2015176672 A JP2015176672 A JP 2015176672A JP 2014050524 A JP2014050524 A JP 2014050524A JP 2014050524 A JP2014050524 A JP 2014050524A JP 2015176672 A JP2015176672 A JP 2015176672A
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- Prior art keywords
- positive electrode
- mol
- active material
- electrode active
- secondary battery
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- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 41
- 239000007774 positive electrode material Substances 0.000 claims abstract description 67
- 239000011575 calcium Substances 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 230000007246 mechanism Effects 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
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- 239000002184 metal Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002800 charge carrier Substances 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 7
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 32
- 239000007773 negative electrode material Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
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- 235000010290 biphenyl Nutrition 0.000 claims description 16
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- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 38
- 229910001416 lithium ion Inorganic materials 0.000 description 38
- 239000010410 layer Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- -1 lithium transition metal Chemical class 0.000 description 15
- 229910052726 zirconium Inorganic materials 0.000 description 15
- 238000000034 method Methods 0.000 description 14
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- 239000002243 precursor Substances 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
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- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
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- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000002905 metal composite material Substances 0.000 description 6
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
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- 239000003792 electrolyte Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000009783 overcharge test Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 239000002356 single layer Substances 0.000 description 2
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- 239000002562 thickening agent Substances 0.000 description 2
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- 238000004804 winding Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Chemical group 0.000 description 1
- 239000011029 spinel Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/578—Devices or arrangements for the interruption of current in response to pressure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
【解決手段】本発明に係る非水電解液二次電池100は、正極活物質層54を含む正極50を備える電極体20と、電極体20に接続された外部端子42と、ガス発生剤を含む非水電解液と、電流遮断機構90とを備える。ガス発生剤の含有量は少なくとも4質量%である。正極活物質層54は、正極活物質として、少なくともジルコニウム(Zr)およびカルシウム(Ca)を構成元素として含む複合酸化物を含んでいる。複合酸化物は、該複合酸化物中の電荷担体となる金属を除く金属元素の合計をモル百分率で100mol%としたとき、Zrを0.1mol%〜0.5mol%、Caを0.1mol%〜0.3mol%の割合で含む。
【選択図】図1
Description
LixNiaCobMncZrdCaeMefO2 (1)
で示される層状結晶構造の複合酸化物である。
ここで、式(1)中のMeは、存在しないか若しくは遷移金属元素,典型金属元素およびホウ素(B)から選択される一種または二種以上の元素である。上記式中のx,a,b,c,d,eおよびfは、0.99≦x≦1.2、0.9≦a+b+c+d+e+f≦1.1、0<a≦0.5、0<b≦0.5、0<c≦0.5、0.001≦d≦0.005、0.001≦e≦0.003、0≦f≦0.01を全て満足する数である。好ましい一態様では、a+b+c+d+e+f=1である。かかる一般式(1)で示される組成の複合酸化物は、初期容量が高く且つ優れた出力特性を実現し得る。
n[C12H16]→(C12H14)n+nH2
・ビフェニル(BP)
n[C12H10]→(C12H8)n+nH2
評価用セルの正極は、次のようにして作製した。まず、正極活物質粉末と、バインダとしてのPVdFと、導電材としてのABとを、これらの材料の質量比が91:3:6となるようにNMP中で混合して、正極活物質層用組成物を調製した。この正極活物質層用組成物を長尺シート状のアルミニウム箔(正極集電体)の両面に帯状に塗布して乾燥することにより、正極集電体の両面に正極活物質層が設けられた正極シートを作製した。正極活物質としては、基本組成LiNi1/3Co1/3Mn1/3O2で表される複合酸化物にZrおよびCaを所定割合で添加したものを使用した。ZrおよびCaの添加量(上記複合酸化物中のLiを除く金属元素(Ni、Co、Mn、ZrおよびCa)の合計を100mol%としたときのモル百分率)は、何れも0.1mol%とした。
正極活物質中のCaの含有量を0.3mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.2mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.2mol%、Caの含有量を0.3mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.5mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.5mol%、Caの含有量を0.3mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.5mol%、Caの含有量を0mol%(即ち非添加)とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.5mol%とし、Caの含有量を0.4mol%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
正極活物質中のZrの含有量を0.5mol%とし、Caの含有量を0.3mol%とした。また、非水電解液に対するガス発生剤の総量は0.6質量%とした。それ以外は実施例1と同様の手順でリチウムイオン二次電池を作製した。
上記各例のリチウムイオン二次電池について、初期容量とIV抵抗とサイクル耐久後容量維持率と過充電試験時における電流遮断機構の作動の有無とを評価した。
各評価用セルについて、1Cの定電流で4.1Vまで充電し、続いて合計充電時間が3時間となるまで定電圧で充電し(CCCV充電)、10分間休止した。次いで、0.33Cの定電流で4.1Vまで充電し(CV充電)、10分間停止した。そして、0.33Cで3.0Vまで放電し、続いて合計放電時間が4時間となるまで定電圧で放電し、10分間停止する(CCCV放電)。上記CCCV放電における放電容量を初期容量とした。結果を表1の該当欄に示す。
各評価用セルについて、初期容量の凡そ60%の充電状態(SOC60%)に調整した後、25℃の環境雰囲気下において、10Cの電流値で10秒間の放電を行い、放電開始から10秒後の電圧値を測定し、IV抵抗を算出した。結果を表1の該当欄に示す。
各評価用セルそれぞれに対し、60℃環境下において、2Cで4.1Vまで充電した後、2Cで3.1Vまで放電を行う充放電サイクルを500回連続して繰り返した。かかるハイレートサイクル耐久後の電池容量を上述した初期容量と同じ条件で測定し、(ハイレートサイクル耐久後の電池容量/初期容量)×100からハイレートサイクル耐久後容量維持率を算出した。結果を表1の該当欄に示す。
上述したハイレートサイクル耐久試験の前後における各評価用セルを用いて、25℃の試験槽中でSOC140%まで充電して過充電状態とする過充電試験を実施した。そして、SOC140%に到達するまでに電流遮断機構(CID)が作動するか否かを確認した。結果を表1の該当欄に示す。SOC140%に到達するまでに電流遮断機構が作動したものを「○」、電流遮断機構が作動しなかったものを「×」で示している。
30 電池ケース
42 正極端子
44 負極端子
50 正極シート
52 正極集電体
54 正極活物質層
60 負極シート
62 負極集電体
64 負極活物質層
70 セパレータ
90 電流遮断機構
100 リチウムイオン二次電池
Claims (4)
- 正極活物質層が正極集電体に保持された正極と、負極活物質層が負極集電体に保持された負極と、前記正極と前記負極との間に介在するセパレータとを備える電極体と、
前記電極体を収容する電池ケースと、
前記電池ケースに設けられ、前記電極体に接続された外部端子と、
前記電池ケースに収容され、予め定められた電圧以上の電圧で反応し、ガスを発生させるガス発生剤を含む非水電解液と、
前記電池ケースの内圧が予め定められた圧力以上に高くなると、前記電極体と前記外部端子との電気的な接続を遮断する電流遮断機構と
を備え、
前記非水電解液全体の質量を100質量%とした場合の前記ガス発生剤の含有量が、少なくとも4質量%であり、
前記正極活物質層は、正極活物質として、少なくともジルコニウム(Zr)およびカルシウム(Ca)を構成元素として含む複合酸化物を含んでおり、
前記複合酸化物は、該複合酸化物中の電荷担体となる金属を除く金属元素の合計をモル百分率で100mol%としたとき、Zrを0.1mol%〜0.5mol%、Caを0.1mol%〜0.3mol%の割合で含む、非水電解液二次電池。 - 前記複合酸化物は、該複合酸化物中の電荷担体を除く金属元素の合計をモル百分率で100mol%としたとき、Zrを0.1mol%〜0.2mol%の割合で含む、請求項1に記載の非水電解液二次電池。
- 前記複合酸化物は、以下の一般式:
LixNiaCobMncZrdCaeMefO2 (1)
(式(1)中のx,a,b,c,d,eおよびfは、
0.99≦x≦1.2、
0.9≦a+b+c+d+e+f≦1.1、
0<a≦0.5、0<b≦0.5、0<c≦0.5、0.001≦d≦0.005、0.001≦e≦0.003、0≦f≦0.01を全て満足する数であり、Meは、存在しないか若しくは遷移金属元素,典型金属元素およびホウ素(B)から選択される一種または二種以上の元素である。)
で示される層状結晶構造の複合酸化物である、請求項1または2に記載の非水電解液二次電池。 - 前記非水電解液は、前記ガス発生剤として、シクロヘキシルベンゼンおよびビフェニルを含んでいる、請求項1〜3の何れか一つに記載の非水電解液二次電池。
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