JP2015005450A - Method for manufacturing nonaqueous electrolyte secondary battery - Google Patents
Method for manufacturing nonaqueous electrolyte secondary battery Download PDFInfo
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- JP2015005450A JP2015005450A JP2013130879A JP2013130879A JP2015005450A JP 2015005450 A JP2015005450 A JP 2015005450A JP 2013130879 A JP2013130879 A JP 2013130879A JP 2013130879 A JP2013130879 A JP 2013130879A JP 2015005450 A JP2015005450 A JP 2015005450A
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- active material
- positive electrode
- electrode active
- negative electrode
- aqueous electrolyte
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000007773 negative electrode material Substances 0.000 claims abstract description 43
- 238000007600 charging Methods 0.000 claims abstract description 39
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- -1 alkali metal cation Chemical class 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 54
- 239000010410 layer Substances 0.000 description 39
- 229910052744 lithium Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 239000010452 phosphate Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 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
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000654 additive 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
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000284 resting effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910014397 LiNi1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 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
- 239000003446 ligand Substances 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect 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
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 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
- 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
- 150000003457 sulfones Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
Abstract
Description
本発明は、非水電解液二次電池に関する。より詳しくは、該電池の製造方法に関する。 The present invention relates to a non-aqueous electrolyte secondary battery. In more detail, it is related with the manufacturing method of this battery.
リチウムイオン電池等の非水電解液二次電池は、既存の電池に比べて軽量かつエネルギー密度が高いことから、近年、いわゆるポータブル電源や車両搭載用の高出力電源等に好ましく利用されている。 Non-aqueous electrolyte secondary batteries such as lithium ion batteries are lighter and have higher energy density than existing batteries, and have recently been preferably used for so-called portable power supplies, high-output power supplies mounted on vehicles, and the like.
非水電解液二次電池では、初期充電の際に非水電解液の一部が負極で還元分解され、負極活物質の表面にその分解物からなる被膜が形成される。これに関連する技術として、特許文献1が挙げられる。特許文献1には、非水電解液中にオキサラトボレート型の化合物(例えば、リチウムジフルオロビス(オキサラト)ホスフェート)を含むことで、活物質の表面に該化合物の配位子を含む被膜を形成し得、従来に比べてサイクル特性や高温貯蔵特性を向上し得る旨が記載されている。 In the non-aqueous electrolyte secondary battery, a part of the non-aqueous electrolyte is reduced and decomposed at the negative electrode during initial charging, and a coating film made of the decomposition product is formed on the surface of the negative electrode active material. Patent document 1 is mentioned as a technique relevant to this. In Patent Document 1, a film containing a ligand of the compound is formed on the surface of an active material by including an oxalatoborate type compound (for example, lithium difluorobis (oxalato) phosphate) in the nonaqueous electrolytic solution. In addition, it is described that the cycle characteristics and the high-temperature storage characteristics can be improved as compared with the prior art.
ところで、非水電解液二次電池の用途のなかには、ハイレートでの充放電(急速充放電)を繰り返す態様で使用されることが想定されるものがある。このような用途向けの非水電解液二次二次電池(例えば車載用途の電池)では、上記のような耐久性に加え、ハイレート特性やハイレート充放電を繰り返しても電池性能の低下が少ないこと(例えば反応抵抗の上昇が少ないこと)が求められる。しかしながら、一般に耐久性とハイレート特性とは相反する特性であり、これらの特性を高いレベルで同時に実現することは困難である。
本発明は、かかる事情に鑑みてなされたものであり、その目的は、オキサラトボレート型化合物添加の効果が好適に発揮され、耐久性(容量維持性)とハイレート特性とを高いレベルで両立可能な非水電解液二次電池を提供することである。関連する他の目的は、生産性や再現性に優れた該電池の製造方法を提供することである。
By the way, some uses of non-aqueous electrolyte secondary batteries are assumed to be used in a mode in which charging / discharging (rapid charging / discharging) at a high rate is repeated. For non-aqueous electrolyte secondary batteries for such applications (for example, batteries for automotive applications), in addition to the durability described above, there is little degradation in battery performance even after repeated high-rate characteristics and high-rate charge / discharge. (For example, there is little increase in reaction resistance). However, generally, durability and high-rate characteristics are contradictory characteristics, and it is difficult to simultaneously realize these characteristics at a high level.
The present invention has been made in view of such circumstances, and its purpose is to suitably exhibit the effect of adding an oxalatoborate type compound, and to achieve both durability (capacity maintenance) and high rate characteristics at a high level. And providing a non-aqueous electrolyte secondary battery. Another related object is to provide a method for producing the battery that is excellent in productivity and reproducibility.
本発明者の知見によれば、充電によってオキサラトボレート型の化合物が分解されると、負極活物質の表面にシュウ酸イオン(C2O4 2−)を含む被膜が形成され、これと同時に、被膜形成に寄与しなかった分解生成物(例えばPO2F2 −)の一部が正極に移動し、正極活物質の表面に吸着し得る。そこで本発明者は、負極活物質の表面に形成される被膜の量を調整し、さらに、正極活物質の表面状態および該表面に吸着する上記分解生成物の量を制御すれば、上述のような課題を解決し得ると考えた。そして、鋭意検討を重ねた結果、オキサラトボレート型化合物の機能をより適切に発揮させて高性能の非水電解液二次電池が得られることを見出し、本発明を完成させた。 According to the knowledge of the present inventors, when the oxalatoborate type compound is decomposed by charging, a film containing oxalate ions (C 2 O 4 2− ) is formed on the surface of the negative electrode active material, and at the same time, Some of the decomposition products (for example, PO 2 F 2 − ) that did not contribute to the film formation may move to the positive electrode and be adsorbed on the surface of the positive electrode active material. Therefore, the present inventor adjusts the amount of the coating formed on the surface of the negative electrode active material, and further controls the surface state of the positive electrode active material and the amount of the decomposition product adsorbed on the surface as described above. Thought that it could solve various problems. As a result of extensive studies, the inventors have found that a high-performance nonaqueous electrolyte secondary battery can be obtained by appropriately exerting the function of the oxalatoborate type compound, and the present invention has been completed.
本発明により提供される非水電解液二次電池の製造方法は、以下の(i)〜(iii)の工程を包含する。
(i)正極活物質を有する正極と、負極活物質を有する負極と、を備える電極体を準備すること。ここで、上記正極活物質としては、DEP(ジブチルフタレート)吸油量が25ml/100g以上48ml/100g以下のものを用いる。
(ii)上記電極体を非水電解液とともに電池ケース内に収容すること。ここで、上記非水電解液には、一般式(1):A+[PX6−2n(C2O4)n]−で示される化合物(以下、単に「P−オキサラト化合物」ということがある。)を、電池の容量1Ahあたり0.01g以上0.5g以下の割合で含ませる。なお、式(1)において、A+はアルカリ金属のカチオンである。Xはハロゲン原子である。nは、1または2または3である。
(iii)上記電極体に対して少なくとも1回の充電処理を行うこと。
The manufacturing method of the nonaqueous electrolyte secondary battery provided by the present invention includes the following steps (i) to (iii).
(I) preparing an electrode body comprising a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material. Here, as the positive electrode active material, one having a DEP (dibutyl phthalate) oil absorption of 25 ml / 100 g or more and 48 ml / 100 g or less is used.
(Ii) The electrode body is accommodated in a battery case together with a non-aqueous electrolyte. Here, the non-aqueous electrolyte includes a compound represented by the general formula (1): A + [PX 6-2n (C 2 O 4 ) n ] − (hereinafter simply referred to as “P-oxalato compound”). Is included at a rate of 0.01 g or more and 0.5 g or less per 1 Ah of battery capacity. In the formula (1), A + is an alkali metal cation. X is a halogen atom. n is 1 or 2 or 3.
(Iii) Perform at least one charge process on the electrode body.
P−オキサラト化合物を含む電池では、充電処理(典型的には初回充電処理)によって該化合物が還元分解され、負極活物質の表面にシュウ酸イオン(C2O4 2−)を含む良質な(緻密で安定性に優れた)被膜が形成される。これにより、負極活物質と非水電解液との界面が安定化され、非水電解液の還元分解を抑制することができる。また、ここで開示される製造方法では、電池容量1AhあたりのP−オキサラト化合物の添加量を規定するため、設計パラメータ(例えば負極活物質層の目付量や厚み、密度等)の変更に柔軟に対処することができる。これにより、負極活物質の表面に最適な量の被膜を安定的に形成することができ、負極の反応抵抗を低く抑えることができる。さらに、DEP吸油量が上記範囲を満たす正極活物質を備えた電池では、正極活物質と非水電解液と親和性に優れ、界面抵抗を低く抑えることができる。また、DEP吸油量が上記範囲を満たす場合、正極活物質の表面に吸着するP−オキサラト化合物の分解生成物の量を抑制することができる。これにより、正極の反応抵抗を一層低く抑えることができる。
したがって、ここで開示される製造方法によれば、以後の充放電における非水電解液の酸化分解および還元分解を高度に抑制することができ、且つ、充放電に伴う抵抗を従来に比べて低減することができる。すなわち、耐久性とハイレート特性とを高いレベルで両立可能な非水電解液二次電池を実現することができる。
In a battery containing a P-oxalato compound, the compound is reduced and decomposed by a charging process (typically, an initial charging process), and a high-quality battery containing oxalate ions (C 2 O 4 2− ) on the surface of the negative electrode active material ( A dense film having excellent stability is formed. Thereby, the interface between the negative electrode active material and the non-aqueous electrolyte is stabilized, and reductive decomposition of the non-aqueous electrolyte can be suppressed. Moreover, in the manufacturing method disclosed here, the amount of P-oxalato compound added per 1Ah of battery capacity is regulated, so that it is flexible to change design parameters (for example, the basis weight, thickness, density, etc. of the negative electrode active material layer). Can be dealt with. Thereby, an optimal amount of a film can be stably formed on the surface of the negative electrode active material, and the reaction resistance of the negative electrode can be kept low. Furthermore, in a battery including a positive electrode active material whose DEP oil absorption amount satisfies the above range, the battery has excellent affinity with the positive electrode active material and the non-aqueous electrolyte, and the interface resistance can be kept low. Moreover, when the DEP oil absorption amount satisfies the above range, the amount of the decomposition product of the P-oxalato compound adsorbed on the surface of the positive electrode active material can be suppressed. Thereby, the reaction resistance of the positive electrode can be further reduced.
Therefore, according to the manufacturing method disclosed herein, the oxidative decomposition and reductive decomposition of the nonaqueous electrolytic solution in the subsequent charging / discharging can be suppressed to a high level, and the resistance accompanying charging / discharging is reduced as compared with the conventional method. can do. That is, it is possible to realize a non-aqueous electrolyte secondary battery capable of achieving both durability and high rate characteristics at a high level.
なお、本明細書において「吸油量」とは、試薬液体としてDBP(ジブチルフタレート)を使用し、JIS K6217−4(2008)に準拠して測定した値をいう。
また、本明細書において「電池の容量」とは、非水電解液二次電池に対して、25℃の温度環境下で、正負極端子間電圧が4.1Vになるまで1/3Cの定電流で充電し(典型的には、続いて定電圧で充電し)た後、正負極端子間電圧が3.0Vになるまで1/3Cの定電流で放電し、続いて電流値が1/3Cとなるまで(あるいは、合計の充電時間が1.5時間となるまで)定電圧で放電した場合のCCCV放電容量(Ah)をいう。
In the present specification, the “oil absorption amount” refers to a value measured using DBP (dibutyl phthalate) as a reagent liquid in accordance with JIS K6217-4 (2008).
Further, in this specification, “battery capacity” is a constant of 1/3 C with respect to the non-aqueous electrolyte secondary battery in a temperature environment of 25 ° C. until the voltage between the positive and negative terminals becomes 4.1V. After charging with a current (typically, charging with a constant voltage), the battery is discharged with a constant current of 1/3 C until the voltage between the positive and negative terminals reaches 3.0 V, and then the current value is 1 / The CCCV discharge capacity (Ah) when discharged at a constant voltage until 3C is reached (or until the total charging time is 1.5 hours).
好適な一態様では、P−オキサラト化合物として、上記一般式(1)中のnが2のものを主体として用いる。ここで、「主体として」とは、上記一般式(1)で示される化合物の全モル数の50モル%以上を、n=2のもの(すなわち、A+[PX4(C2O4)2]−)とすることをいう。なかでも、n=2のものを80モル%以上(典型的には90モル%以上、例えば95モル%以上)用いることが好ましく、実質的にn=2のものを用いることが特に好ましい。
また、好適な他の一態様では、上記一般式(1)中のXがフッ素原子(F)である。すなわち、P−オキサラト化合物は、一般式:A+[PF6−2n(C2O4)n]−(式中、A+,nは上記一般式(1)と同様。)で表される化合物である。フッ素原子は電気陰性度が高いため還元分解され易く、また、ハロゲンの中でもイオン半径が最も小さいため、負極活物質表面に低抵抗で良質な被膜を好適に形成することができる。したがって、本願発明の効果をより高いレベルで発揮することができる。
In a preferred embodiment, as the P-oxalato compound, those in which n is 2 in the general formula (1) are mainly used. Here, “as the main component” means that 50 mol% or more of the total number of moles of the compound represented by the general formula (1) is n = 2 (that is, A + [PX 4 (C 2 O 4 ) 2 ] - ). Especially, it is preferable to use 80 mol% or more (typically 90 mol% or more, for example, 95 mol% or more) of n = 2, and it is particularly preferable to use n = 2.
In another preferred embodiment, X in the general formula (1) is a fluorine atom (F). That is, the P-oxalato compound is represented by the general formula: A + [PF 6-2n (C 2 O 4 ) n ] − (wherein A + and n are the same as those in the general formula (1)). A compound. Since fluorine atoms have high electronegativity, they are easily reductively decomposed, and since the ion radius is the smallest among the halogens, it is possible to suitably form a high-quality film with low resistance on the surface of the negative electrode active material. Therefore, the effect of the present invention can be exhibited at a higher level.
好適な一態様では、上記正極活物質として、DEP吸油量が30ml/100g以上48ml/100g以下のものを用いる。上記DEP吸油量の範囲を満たす正極活物質を用いることで、例えばハイレート充放電を長期に渡って繰り返した場合であっても、電池抵抗が上昇し難く、優れた耐久性(ハイレートサイクル特性)を実現することができる。 In a preferred embodiment, the positive electrode active material has a DEP oil absorption of 30 ml / 100 g to 48 ml / 100 g. By using a positive electrode active material that satisfies the above DEP oil absorption range, for example, even when high-rate charge / discharge is repeated over a long period of time, battery resistance is unlikely to increase and excellent durability (high-rate cycle characteristics) is achieved. Can be realized.
ここで開示される技術の他の側面として、非水電解液二次電池組立体が提供される。かかる電池組立体は、充電処理が施される前の状態であって、電極体と非水電解液とを有している。上記電極体は、正極活物質を有する正極と、負極活物質を有する負極と、を備えている。そして、上記正極活物質のDEP吸油量は25ml/100g以上48ml/100g以下である。また、上記非水電解液には、一般式(1):A+[PX6−2n(C2O4)n]−で示される化合物が、電池の容量1Ahあたり0.01g以上0.5g以下の割合で含まれている。式(1)中において、A+はアルカリ金属のカチオンである。Xはハロゲン原子である。nは、1または2または3である。
なお、本明細書において「電池組立体」とは、充電処理が施される前の状態であって該充電処理に先立った段階にまで組み立てられているもの全般をいい、電池の種類や構成等は特に限定されない。例えば、電池ケースは封口前であってもよいし、封口後であってもよい。
As another aspect of the technology disclosed herein, a non-aqueous electrolyte secondary battery assembly is provided. Such a battery assembly is in a state before being charged, and has an electrode body and a non-aqueous electrolyte. The electrode body includes a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material. And the DEP oil absorption of the said positive electrode active material is 25 ml / 100g or more and 48 ml / 100g or less. The non-aqueous electrolyte contains a compound represented by the general formula (1): A + [PX 6-2n (C 2 O 4 ) n ] − in an amount of 0.01 g to 0.5 g per 1 Ah of battery capacity. It is included in the following proportions. In the formula (1), A + is an alkali metal cation. X is a halogen atom. n is 1 or 2 or 3.
In the present specification, the “battery assembly” means a state in which the battery has been assembled up to a stage prior to the charging process and prior to the charging process. Is not particularly limited. For example, the battery case may be before sealing or after sealing.
上記電池組立体を充電処理して得られる非水電解液二次電池、あるいは、ここで開示される製造方法によって製造された非水電解液二次電池は、耐久性とハイレート特性(特にはハイレートサイクル特性)とを高いレベルで両立可能なことを特徴とする。
したがって、かかる特徴を活かして、高出力密度や高耐久性が要求される用途で好適に使用することができる。このような用途としては、例えばハイブリッド車両等の動力源(車両駆動用電源)が挙げられる。換言すれば、ここで開示される他の側面として上記非水電解液二次電池を備えた車両が提供される。なお、車両に搭載される電池は、該電池が複数個相互に電気的に接続されてなる組電池の形態であり得る。
The non-aqueous electrolyte secondary battery obtained by charging the battery assembly or the non-aqueous electrolyte secondary battery manufactured by the manufacturing method disclosed herein has durability and high-rate characteristics (particularly, high-rate characteristics). Cycle characteristics) at a high level.
Therefore, taking advantage of such characteristics, it can be suitably used in applications that require high power density and high durability. As such an application, for example, a power source (vehicle drive power source) such as a hybrid vehicle can be cited. In other words, as another aspect disclosed herein, a vehicle including the nonaqueous electrolyte secondary battery is provided. Note that the battery mounted on the vehicle may be in the form of an assembled battery in which a plurality of the batteries are electrically connected to each other.
以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項(例えば、正極活物質のDEP吸油量や非水電解液中のP−オキサラト化合物の含有量)以外の事柄であって本発明の実施に必要な事柄(例えば、本発明を特徴付けない電池の一般的な製造プロセス)は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。 Hereinafter, preferred embodiments of the present invention will be described. In addition, it is matters other than the matters specifically mentioned in the present specification (for example, the DEP oil absorption amount of the positive electrode active material and the content of the P-oxalato compound in the non-aqueous electrolyte solution) and are necessary for the implementation of the present invention. Matters (eg, a general manufacturing process of a battery that does not characterize the present invention) can be understood as a matter of design by those skilled in the art based on the prior art in the field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
≪非水電解液二次電池の製造方法≫
ここで開示される非水電解液二次電池の製造方法は、大まかに言って、(i)準備工程;(ii)電池組立体構築工程;(iii)充電処理工程;を包含する。なお(i),(ii)は、電池組立体の製造方法としても把握し得る。以下、各工程について順に説明する。
≪Method for manufacturing non-aqueous electrolyte secondary battery≫
The method for producing a non-aqueous electrolyte secondary battery disclosed herein roughly includes (i) a preparation step; (ii) a battery assembly construction step; and (iii) a charging treatment step. In addition, (i) and (ii) can also be grasped as a method for manufacturing a battery assembly. Hereinafter, each process is demonstrated in order.
<i.準備工程>
準備工程では、正極活物質を有する正極と、負極活物質を有する負極と、を備える電極体を準備する。電極体作製に用いる材料やプロセスは、所定の性状を満たす正極活物質を用いること以外特に限定なく、従来と同様でよい。かかる電極体は、例えば、ここで開示されるDEP吸油量の範囲を満たす正極活物質を備えた正極と、負極活物質を備えた負極とを、両者の直接接触を防ぐ絶縁層を介して対向させ、積層することで作製し得る。
<I. Preparation process>
In the preparation step, an electrode body including a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material is prepared. There are no particular limitations on the materials and processes used to produce the electrode body, except that a positive electrode active material that satisfies the predetermined properties is used, and may be the same as in the past. Such an electrode body, for example, faces a positive electrode including a positive electrode active material that satisfies the range of DEP oil absorption disclosed herein and a negative electrode including a negative electrode active material through an insulating layer that prevents direct contact therebetween. And can be produced by stacking.
<正極>
正極は、上記性状の正極活物質を備えるものであれば特に限定されないが、典型的には、正極集電体上に当該正極活物質を含む正極活物質層が固着された形態である。このような正極は、例えば、以下のような方法で作製することができる。先ず、正極活物質と導電材とバインダ(結着剤)とを適当な溶媒(例えばN−メチル−2−ピロリドン)に分散させ、ペースト状またはスラリー状の組成物を調製する。次に、この組成物を正極集電体の表面に付与した後、乾燥によって溶媒を除去する。これにより、正極集電体上に正極活物質層を備えた正極を作製することができる。
正極集電体としては、導電性の良好な金属(例えばアルミニウム、ニッケル、チタン、ステンレス鋼等)からなる導電性部材を好適に使用することができる。
<Positive electrode>
The positive electrode is not particularly limited as long as it includes the positive electrode active material having the above properties, but typically, the positive electrode active material layer containing the positive electrode active material is fixed on the positive electrode current collector. Such a positive electrode can be produced, for example, by the following method. First, a positive electrode active material, a conductive material, and a binder (binder) are dispersed in a suitable solvent (for example, N-methyl-2-pyrrolidone) to prepare a paste-like or slurry-like composition. Next, after applying this composition to the surface of the positive electrode current collector, the solvent is removed by drying. Thereby, the positive electrode provided with the positive electrode active material layer on the positive electrode current collector can be produced.
As the positive electrode current collector, a conductive member made of a metal having good conductivity (for example, aluminum, nickel, titanium, stainless steel, etc.) can be preferably used.
正極活物質としては、DEP吸油量が25ml/100g以上48ml/100g以下のものを用いることができる。正極活物質のDEP吸油量を25ml/100g以上(典型的には26ml/100g以上、例えば28ml/100g以上)とすることで、非水電解液との親和性を向上することができる。これにより、界面抵抗を低く抑えることができ、ハイレート特性の向上を実現することができる。また、正極活物質のDEP吸油量を48ml/100g以下(典型的には48ml/100g未満、例えば47.5ml/100g以下)とすることで、正極活物質の表面に吸着し得るP−オキサラト化合物由来の分解生成物(例えばPO2X2 −イオン)の量を抑制することができる。これにより、充放電時の反応抵抗を一層低減することができる。好適な一態様では、DEP吸油量が30ml/100g以上48ml/100g以下の正極活物質を用いる。これにより、優れたハイレートサイクル特性を実現することができ、本願発明の効果を更にレベルで発揮することができる。なお、正極活物質のDEP吸油量は、例えば、正極活物質の製造に用いる原材料の種類や、正極活物質の物理・化学的性状(例えば、平均粒径や比表面積、酸性官能基の含有量等)を制御することによって、上述の範囲に調整することができる。一般的には、他の条件(活物質の種類や粒子構造等)が同様であれば、粒径が小さくおよび/または比表面積が大きくなるほど、DEP吸油量は大きくなる傾向にある。 As the positive electrode active material, one having a DEP oil absorption of 25 ml / 100 g or more and 48 ml / 100 g or less can be used. By setting the DEP oil absorption amount of the positive electrode active material to 25 ml / 100 g or more (typically 26 ml / 100 g or more, for example, 28 ml / 100 g or more), the affinity with the non-aqueous electrolyte can be improved. As a result, the interface resistance can be kept low, and an improvement in the high rate characteristics can be realized. Moreover, the P-oxalato compound which can adsorb | suck to the surface of a positive electrode active material by making DEP oil absorption amount of a positive electrode active material into 48 ml / 100g or less (typically less than 48 ml / 100g, for example, 47.5 ml / 100g or less). it is possible to suppress the amount of - decomposition products from (ion eg PO 2 X 2). Thereby, the reaction resistance at the time of charging / discharging can be reduced further. In a preferred embodiment, a positive electrode active material having a DEP oil absorption of 30 ml / 100 g or more and 48 ml / 100 g or less is used. Thereby, excellent high rate cycle characteristics can be realized, and the effects of the present invention can be exhibited at a further level. The DEP oil absorption amount of the positive electrode active material is, for example, the type of raw material used for the production of the positive electrode active material, the physical / chemical properties of the positive electrode active material (for example, average particle diameter, specific surface area, content of acidic functional groups) Etc.) can be adjusted to the above-mentioned range. In general, if the other conditions (type of active material, particle structure, etc.) are the same, the DEP oil absorption tends to increase as the particle size decreases and / or the specific surface area increases.
正極活物質としては、上記DEP吸油量の範囲を満たす限りにおいて特に限定されず、非水電解液二次電池の正極活物質として使用し得ることが知られているものを、1種または2種以上採用することができる。好適例として、層状系、スピネル系等のリチウム複合金属酸化物(例えば、LiNiO2、LiCoO2、LiFeO2、LiMn2O4、LiNi0.5Mn1.5O4,LiCrMnO4、LiFePO4等)が挙げられる。なかでも、構成元素としてLi,Ni,CoおよびMnを含む、層状構造(典型的には、六方晶系に属する層状岩塩型構造)のリチウムニッケルコバルトマンガン複合酸化物(例えば、LiNi1/3Co1/3Mn1/3O2)は、熱安定性に優れ、且つ高いエネルギー密度を実現し得るため好ましく用いることができる。 The positive electrode active material is not particularly limited as long as it satisfies the range of the DEP oil absorption amount, and one or two types of those known to be usable as the positive electrode active material of the nonaqueous electrolyte secondary battery are used. The above can be adopted. Preferable examples include layered and spinel-based lithium composite metal oxides (for example, LiNiO 2 , LiCoO 2 , LiFeO 2 , LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiCrMnO 4 , LiFePO 4, etc. ). Among them, lithium nickel cobalt manganese composite oxide (for example, LiNi 1/3 Co) having a layered structure (typically a layered rock salt structure belonging to a hexagonal system) containing Li, Ni, Co, and Mn as constituent elements. 1/3 Mn 1/3 O 2 ) is preferably used because it is excellent in thermal stability and can realize a high energy density.
ここで、リチウムニッケルコバルトマンガン複合酸化物とは、Li,Ni,CoおよびMnのみを構成金属元素とする酸化物のほか、Li,Ni,CoおよびMn以外に他の少なくとも1種の金属元素(すなわち、Li,Ni,CoおよびMn以外の遷移金属元素および/または典型金属元素)を含む酸化物をも包含する意味である。かかる金属元素は、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)、チタン(Ti)、ジルコニウム(Zr)、バナジウム(V)、ニオブ(Nb)、クロム(Cr)、モリブデン(Mo)、タングステン(W)、鉄(Fe)、ロジウム(Rh)、パラジウム(Pb)、白金(Pt)、銅(Cu)、亜鉛(Zn)、ホウ素(B)、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、スズ(Sn)、ランタン(La)、セリウム(Ce)のうちの1種または2種以上の元素であり得る。これらの金属元素の添加量(配合量)は特に限定されないが、通常0.01質量%〜5質量%(例えば0.05質量%〜2質量%、典型的には0.1質量%〜0.8質量%)であり得る。 Here, the lithium nickel cobalt manganese composite oxide is an oxide containing only Li, Ni, Co and Mn as constituent metal elements, and at least one other metal element in addition to Li, Ni, Co and Mn ( That is, it is meant to include oxides containing transition metal elements and / or typical metal elements other than Li, Ni, Co and Mn. Such metal elements include magnesium (Mg), calcium (Ca), strontium (Sr), titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), chromium (Cr), molybdenum (Mo), Tungsten (W), iron (Fe), rhodium (Rh), palladium (Pb), platinum (Pt), copper (Cu), zinc (Zn), boron (B), aluminum (Al), gallium (Ga), It may be one or more elements of indium (In), tin (Sn), lanthanum (La), and cerium (Ce). The addition amount (blending amount) of these metal elements is not particularly limited, but is usually 0.01% by mass to 5% by mass (for example, 0.05% by mass to 2% by mass, typically 0.1% by mass to 0% by mass). 8 mass%).
正極活物質の性状は特に限定されないが、通常、平均粒径が0.5μm〜20μm程度(典型的には1μm〜15μm程度、例えば2μm〜10μm程度)の粒子状のものを好ましく使用し得る。また、BET比表面積は、通常、0.1m2/g〜30m2/g程度であり、典型的には0.2m2/g〜10m2/g程度、例えば0.5m2/g〜3m2/g程度のものを好ましく使用し得る。正極活物質の性状が上記範囲にある場合、上記DEP吸油量の範囲を好適に実現することができる。また、正極活物質層内に適度な空隙を確保することができるため、非水電解液を浸漬させ易く、より高いハイレート特性を実現することができる。
なお、本明細書中において「平均粒径」とは、レーザ回折・光散乱法に基づく粒度分布測定により測定した体積基準の粒度分布において、微粒子側からの累積50%に相当する粒径(すなわち、D50粒径。メジアン径。)をいう。また、本明細書中において「比表面積」とは、吸着質として窒素(N2)ガスを用いたガス吸着法(定容量式吸着法)によって測定されたガス吸着量を、BET法(例えば、BET1点法)で解析することによって算出した値をいう。
The property of the positive electrode active material is not particularly limited, but usually a particulate material having an average particle diameter of about 0.5 μm to 20 μm (typically about 1 μm to 15 μm, for example, about 2 μm to 10 μm) can be preferably used. Further, BET specific surface area is usually from 0.1m 2 / g~30m 2 / g approximately, typically 0.2m 2 / g~10m 2 / g approximately, for example, 0.5m 2 / g~3m Those of about 2 / g can be preferably used. When the property of the positive electrode active material is in the above range, the above DEP oil absorption range can be suitably realized. Moreover, since a moderate space | gap can be ensured in a positive electrode active material layer, it is easy to immerse a non-aqueous electrolyte, and a higher high-rate characteristic can be implement | achieved.
In the present specification, the “average particle diameter” means a particle diameter corresponding to 50% cumulative from the fine particle side in a volume-based particle size distribution measured by particle size distribution measurement based on a laser diffraction / light scattering method (that is, , D 50 particle size, median diameter). Further, in this specification, the “specific surface area” means a gas adsorption amount measured by a gas adsorption method (fixed capacity adsorption method) using nitrogen (N 2 ) gas as an adsorbate, and a BET method (for example, This is a value calculated by analyzing with the BET 1-point method.
導電材としては、例えば、カーボンブラック(典型的にはアセチレンブラック、ケッチェンブラック)、活性炭、黒鉛、炭素繊維等の炭素材料を好適に用いることができる。バインダとしては、例えば、ポリフッ化ビニリデン(PVdF)等のハロゲン化ビニル樹脂;ポリエチレンオキサイド(PEO)等のポリアルキレンオキサイド;等のポリマー材料を好適に用いることができる。また、本発明の効果を著しく損なわない限りにおいて、上記材料に加えて各種添加剤(例えば、過充電時にガスを発生させる無機化合物、分散剤、増粘剤等)を使用することもできる。 As the conductive material, for example, carbon materials such as carbon black (typically acetylene black and ketjen black), activated carbon, graphite, and carbon fiber can be suitably used. As the binder, for example, a polymer material such as a vinyl halide resin such as polyvinylidene fluoride (PVdF); a polyalkylene oxide such as polyethylene oxide (PEO); or the like can be suitably used. In addition to the above materials, various additives (for example, inorganic compounds that generate gas during overcharge, dispersants, thickeners, etc.) can be used as long as the effects of the present invention are not significantly impaired.
正極活物質層全体に占める正極活物質の割合は、凡そ60質量%以上(典型的には60質量%〜99質量%)とすることが適当であり、通常は凡そ70質量%〜95質量%であることが好ましい。導電材を使用する場合、正極活物質層全体に占める導電材の割合は、例えば凡そ2質量%〜20質量%とすることができ、通常は凡そ3質量%〜10質量%とすることが好ましい。バインダを使用する場合、正極活物質層全体に占めるバインダの割合は、例えば凡そ0.5質量%〜10質量%とすることができ、通常は凡そ1質量%〜5質量%とすることが好ましい。 The proportion of the positive electrode active material in the entire positive electrode active material layer is suitably about 60% by mass or more (typically 60% by mass to 99% by mass), and usually about 70% by mass to 95% by mass. It is preferable that In the case of using a conductive material, the ratio of the conductive material in the entire positive electrode active material layer can be, for example, about 2% by mass to 20% by mass, and usually about 3% by mass to 10% by mass is preferable. . When using a binder, the ratio of the binder to the whole positive electrode active material layer can be, for example, about 0.5% by mass to 10% by mass, and usually about 1% by mass to 5% by mass is preferable. .
<負極>
負極は、負極活物質を有するものであれば特に限定されないが、典型的には負極集電体上に負極活物質を含む負極活物質層が固着された形態である。このような負極は、例えば、上記正極の場合と同様に作製することができる。
負極集電体としては、導電性の良好な金属(例えば、銅、ニッケル、チタン、ステンレス鋼等)からなる導電性部材を好適に使用することができる。
<Negative electrode>
The negative electrode is not particularly limited as long as it has a negative electrode active material, but typically, the negative electrode active material layer containing the negative electrode active material is fixed on the negative electrode current collector. Such a negative electrode can be produced, for example, in the same manner as in the case of the positive electrode.
As the negative electrode current collector, a conductive member made of a metal having good conductivity (for example, copper, nickel, titanium, stainless steel, etc.) can be suitably used.
負極活物質としては特に限定されず、非水電解液二次電池の負極活物質として使用し得ることが知られているものを、1種または2種以上使用することができる。好適例として、黒鉛(グラファイト)、難黒鉛化炭素(ハードカーボン)、易黒鉛化炭素(ソフトカーボン)、カーボンナノチューブ等の炭素材料が挙げられる。なかでも、導電性に優れ、高いエネルギー密度が得られることから、天然黒鉛や人造黒鉛等の黒鉛系材料(特には天然黒鉛)を好ましく用いることができる。 It does not specifically limit as a negative electrode active material, What can be used as a negative electrode active material of a nonaqueous electrolyte secondary battery can use 1 type (s) or 2 or more types. Preferable examples include carbon materials such as graphite (graphite), non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), and carbon nanotubes. Especially, since it is excellent in electroconductivity and a high energy density is obtained, graphite-type materials (especially natural graphite), such as natural graphite and artificial graphite, can be used preferably.
バインダとしては、例えば、スチレンブタジエンゴム(SBR)、ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン(PTFE)等のポリマー材料を好適に用いることができる。また、本発明の効果を著しく損なわない限りにおいて、上記材料に加えて各種添加剤(例えば、増粘剤、分散剤、導電材等)を使用することもできる。例えば、増粘剤としては、カルボキシメチルセルロース(CMC)やメチルセルロース(MC)等を用いることができる。 As the binder, for example, a polymer material such as styrene butadiene rubber (SBR), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), or the like can be suitably used. In addition to the above materials, various additives (for example, thickeners, dispersants, conductive materials, etc.) can be used as long as the effects of the present invention are not significantly impaired. For example, carboxymethylcellulose (CMC), methylcellulose (MC), etc. can be used as the thickener.
負極活物質層全体に占める負極活物質の割合は、凡そ50質量%以上とすることが適当であり、通常は90質量%〜99質量%(例えば95質量%〜99質量%)とすることが好ましい。バインダを使用する場合には、負極活物質層全体に占めるバインダの割合は例えば凡そ1質量%〜10質量%とすることができ、通常は凡そ1質量%〜5質量%とすることが好ましい。増粘剤等の各種添加剤を使用する場合には、負極活物質層全体に占める添加剤の割合は例えば凡そ1質量%〜10質量%とすることができ、通常は凡そ1質量%〜5質量%とすることが好ましい。 The proportion of the negative electrode active material in the entire negative electrode active material layer is suitably about 50% by mass or more, and is usually 90% by mass to 99% by mass (eg, 95% by mass to 99% by mass). preferable. When using a binder, the ratio of the binder to the whole negative electrode active material layer can be, for example, about 1% by mass to 10% by mass, and usually about 1% by mass to 5% by mass is preferable. When various additives such as a thickener are used, the ratio of the additive to the whole negative electrode active material layer can be, for example, about 1% by mass to 10% by mass, and usually about 1% by mass to 5%. It is preferable to set it as the mass%.
<絶縁層>
上記正極および上記負極の直接接触を防ぐ絶縁層としては、典型的には、セパレータを用いることができる。セパレータとしては特に限定されず、正極活物質層と負極活物質層とを絶縁するとともに非水電解液の保持機能やシャットダウン機能を有するものであればよい。好適例として、ポリエチレン(PE)、ポリプロピレン(PP)、ポリエステル、セルロース、ポリアミド等の樹脂から成る多孔質樹脂シート(フィルム)が挙げられる。かかる多孔質樹脂シートは、単層構造であってもよく、二層以上の積層構造(例えば、PE層の両面にPP層が積層された三層構造)であってもよい。また、セパレータは上記多孔性樹脂シートの片面または両面(典型的には片面)に多孔質の耐熱層を備える構成であってもよい。かかる多孔質耐熱層は、例えば無機材料(アルミナ粒子等の無機フィラー類を好ましく採用し得る。)とバインダとを含む層であり得る。あるいは、絶縁性を有する樹脂粒子(例えば、ポリエチレン、ポリプロピレン等の粒子)を含む層であり得る。
<Insulating layer>
As the insulating layer for preventing direct contact between the positive electrode and the negative electrode, a separator can be typically used. It does not specifically limit as a separator, What is necessary is just to have the holding | maintenance function and shutdown function of a nonaqueous electrolyte while insulating a positive electrode active material layer and a negative electrode active material layer. Preferable examples include porous resin sheets (films) made of a resin such as polyethylene (PE), polypropylene (PP), polyester, cellulose, and polyamide. Such a porous resin sheet may have a single-layer structure or a laminated structure of two or more layers (for example, a three-layer structure in which PP layers are laminated on both sides of a PE layer). Moreover, the structure which equips the single side | surface or both surfaces (typically single side | surface) of the said porous resin sheet with a porous heat resistant layer may be sufficient as a separator. Such a porous heat-resistant layer can be, for example, a layer containing an inorganic material (inorganic fillers such as alumina particles can be preferably employed) and a binder. Alternatively, it may be a layer containing insulating resin particles (for example, particles of polyethylene, polypropylene, etc.).
<ii.電池組立体構築工程>
次いで、電池組立体構築工程では、上記電極体を非水電解液とともに電池ケース内に収容する。電池ケースとしては、例えばアルミニウム等の軽量な金属材製のものを好適に採用することができる。非水電解液は、常温(例えば25℃)で液状を呈する。好ましい一態様では、電池の使用環境下(例えば0℃〜60℃の温度環境下)で常に液状を呈する。
ここで開示される製造方法において、非水電解液には、少なくとも、非水溶媒と、一般式(1):A+[PX6−2n(C2O4)n]−で示される化合物(P−オキサラト化合物)とを含ませる。
<Ii. Battery assembly construction process>
Next, in the battery assembly construction process, the electrode body is accommodated in the battery case together with the non-aqueous electrolyte. As the battery case, for example, a lightweight metal material such as aluminum can be preferably used. The non-aqueous electrolyte exhibits a liquid state at normal temperature (for example, 25 ° C.). In a preferred embodiment, it always exhibits a liquid state under the usage environment of the battery (for example, in a temperature environment of 0 ° C. to 60 ° C.).
In the production method disclosed herein, the non-aqueous electrolyte includes at least a non-aqueous solvent and a compound represented by the general formula (1): A + [PX 6-2n (C 2 O 4 ) n ] − ( P-oxalato compound).
<P−オキサラト化合物>
上記式(1)中において、A+は、Li、Na、K等のアルカリ金属のカチオンである。あるいは、Be、Mg、Ca等のアルカリ土類金属のカチオン;プロトン;テトラブチルアンモニウムイオン、テトラエチルアンモニウムイオン等のテトラアルキルアンモニウムイオン;トリエチルメチルアンモニウムイオン等のトリアルキルアンモニウムイオン;等であり得る。好適な一態様では、A+は、リチウムのカチオン(Li+)である。また、Xは、F、Cl、Br等のハロゲン原子である。好適な一態様では、Xは、フッ素原子(F)である。また、nは、1または2または3である。好適な一態様では、n=2である。換言すれば、P−オキサラト化合物として、一般式:A+[PX4(C2O4)2]−(式中、A+,nは上記一般式(1)と同様。)で示される化合物を用いることが好ましい。
<P-oxalato compound>
In the above formula (1), A + is a cation of an alkali metal such as Li, Na, or K. Alternatively, it may be a cation of an alkaline earth metal such as Be, Mg, or Ca; a proton; a tetraalkylammonium ion such as a tetrabutylammonium ion or a tetraethylammonium ion; a trialkylammonium ion such as a triethylmethylammonium ion; In a preferred embodiment, A + is a lithium cation (Li + ). X is a halogen atom such as F, Cl, or Br. In a preferred embodiment, X is a fluorine atom (F). N is 1 or 2 or 3. In a preferred embodiment, n = 2. In other words, as the P-oxalato compound, a compound represented by the general formula: A + [PX 4 (C 2 O 4 ) 2 ] − (wherein A + and n are the same as those in the general formula (1)). Is preferably used.
P−オキサラト化合物は、少なくとも一つのシュウ酸イオン(C2O4 2−)がリン(P)に配位した構造部分を有するオキサラト錯体化合物である。非水電解液中にP−オキサラト化合物を含むことにより、後述する充電処理工程において、負極活物質の表面に良質な被膜を形成することができる。このような化合物としては、公知の方法により作製したもの、あるいは市販品の購入等により入手したものを特に限定せず1種または2種以上用いることができる。具体例として、下式(I)で示されるリチウムテトラフルオロ(オキサラト)ホスフェート(Li+〔PF4(C2O4)〕−)、下式(II)で示されるリチウムジフルオロビス(オキサラト)ホスフェート(Li+〔PF2(C2O4)2〕−)、下式(III)で示されるリチウムトリス(オキサラト)ホスフェート(Li+〔P(C2O4)3〕−)等が挙げられる。 The P-oxalato compound is an oxalato complex compound having a structural portion in which at least one oxalate ion (C 2 O 4 2− ) is coordinated to phosphorus (P). By including the P-oxalato compound in the non-aqueous electrolyte, a good-quality film can be formed on the surface of the negative electrode active material in the charge treatment step described later. As such a compound, those prepared by a known method or those obtained by purchasing a commercially available product are not particularly limited, and one or more kinds thereof can be used. Specific examples include lithium tetrafluoro (oxalato) phosphate (Li + [PF 4 (C 2 O 4 )] − ) represented by the following formula (I) and lithium difluorobis (oxalato) phosphate represented by the following formula (II). (Li + [PF 2 (C 2 O 4 ) 2 ] − ), lithium tris (oxalato) phosphate (Li + [P (C 2 O 4 ) 3 ] − ) represented by the following formula (III), and the like. .
好適な一態様では、上記式(II)で示されるリチウムジフルオロビス(オキサラト)ホスフェートを主体として(すなわち50モル%以上)用いる。なかでも、リチウムジフルオロビス(オキサラト)ホスフェートを70モル%以上(典型的には80モル%以上、例えば90モル%以上)用いることが好ましく、実質的にリチウムジフルオロビス(オキサラト)ホスフェートからなるP−オキサラト化合物を用いることが特に好ましい。なお、市販品のリチウムジフルオロビス(オキサラト)ホスフェートは、上記式(I)で示されるリチウムテトラフルオロ(オキサラト)ホスフェートが数モル%程度(典型的には5モル%以下、例えば3%モル以下)含み得る。 In a preferred embodiment, lithium difluorobis (oxalato) phosphate represented by the above formula (II) is mainly used (that is, 50 mol% or more). Among these, it is preferable to use lithium difluorobis (oxalato) phosphate in an amount of 70 mol% or more (typically 80 mol% or more, for example, 90 mol% or more), and P— consisting essentially of lithium difluorobis (oxalato) phosphate. It is particularly preferable to use an oxalato compound. The commercially available lithium difluorobis (oxalato) phosphate is about several mol% of lithium tetrafluoro (oxalato) phosphate represented by the above formula (I) (typically 5 mol% or less, for example, 3% mol or less). May be included.
P−オキサラト化合物の添加量は、電池の容量1Ahあたり0.01g以上(典型的には0.015g以上)であって0.5g以下(典型的には0.48g以下)の割合とする。上記添加量の範囲とすることで、負極活物質表面の被膜が不足して耐久性が低下したり、負極活物質表面の被膜が過剰となって電池抵抗が増大したりすることを防止することができる。このため、負極活物質の表面に最適な量の被膜を安定して形成することができる。また、電池容量1Ahあたりの添加量を規定することで、設計パラメータの変更に柔軟に対処することができ、より迅速かつ精度よく最適な量を添加することができる。このことは、生産性や作業性の観点からも好ましい。好適な一態様では、非水電解液中にP−オキサラト化合物を0.01g/Ah以上(典型的には0.015g/Ah以上)であって0.4g/Ah以下(典型的には0.35g/Ah以下、例えば0.32g/Ah以下)とする。これにより、例えば、ハイレート充放電を長期間繰り返した場合であっても電池抵抗の上昇が生じ難く、ハイレートサイクル特性に優れた電池を実現することができる。したがって、本願発明の効果をより高いレベルで発揮することができる。 The amount of the P-oxalato compound added is 0.01 g or more (typically 0.015 g or more) and 0.5 g or less (typically 0.48 g or less) per 1 Ah of battery capacity. By setting the amount within the above range, it is possible to prevent durability from being reduced due to insufficient coating on the surface of the negative electrode active material, or battery resistance from being increased due to excessive coating on the surface of the negative electrode active material. Can do. For this reason, an optimal amount of the film can be stably formed on the surface of the negative electrode active material. In addition, by defining the amount of addition per battery capacity 1 Ah, it is possible to flexibly cope with changes in design parameters, and the optimum amount can be added more quickly and accurately. This is also preferable from the viewpoint of productivity and workability. In a preferred embodiment, the P-oxalato compound is 0.01 g / Ah or more (typically 0.015 g / Ah or more) and 0.4 g / Ah or less (typically 0 or less) in the non-aqueous electrolyte. .35 g / Ah or less, for example, 0.32 g / Ah or less). Thereby, for example, even when high-rate charging / discharging is repeated for a long period of time, it is difficult to increase battery resistance, and a battery with excellent high-rate cycle characteristics can be realized. Therefore, the effect of the present invention can be exhibited at a higher level.
<非水溶媒>
非水溶媒としては特に限定されず、一般的な非水電解液二次電池の電解液に用いられる各種のカーボネート類、エーテル類、エステル類、ニトリル類、スルホン類、ラクトン類等の有機溶媒を用いることができる。好適な一態様では、カーボネート類を主体とする非水溶媒を用いる。具体的には、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ジエチルカーボネート(DEC)、ジメチルカーボネート(DMC)、エチルメチルカーボネート(EMC)等を好適に用いることができる。
<Nonaqueous solvent>
The non-aqueous solvent is not particularly limited, and various organic solvents such as carbonates, ethers, esters, nitriles, sulfones, and lactones used in the electrolyte of general non-aqueous electrolyte secondary batteries are used. Can be used. In a preferred embodiment, a non-aqueous solvent mainly composed of carbonates is used. Specifically, ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or the like can be preferably used.
<支持塩>
好適な一態様では、非水電解液中に、上述のP−オキサラト化合物に加えて、非水電解液二次電池の支持塩として使用し得ることが知られている各種の材料を1種または2種以上含む。支持塩としては、電荷担体(例えば、リチウムイオン、ナトリウムイオン、マグネシウムイオン等。リチウムイオン二次電池ではリチウムイオン。)を含むものであれば特に限定されない。電荷担体がリチウムイオンの場合は、LiPF6、LiBF4、LiClO4、LiAsF6、Li(CF3SO2)2N、LiCF3SO3等のリチウム塩が例示される。特に好ましい支持塩としてLiPF6が挙げられる。また、非水電解液は上記支持塩の濃度が0.7mol/L〜1.3mol/Lの範囲内となるように調製することが好ましい。
<Supporting salt>
In a preferred embodiment, in addition to the P-oxalato compound described above, one or more of various materials known to be used as a supporting salt for a non-aqueous electrolyte secondary battery are used in the non-aqueous electrolyte. Contains 2 or more. The supporting salt is not particularly limited as long as it contains a charge carrier (for example, lithium ion, sodium ion, magnesium ion, etc., lithium ion in a lithium ion secondary battery). When the charge carrier is lithium ion, lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li (CF 3 SO 2 ) 2 N, LiCF 3 SO 3 are exemplified. LiPF 6 may be mentioned as particularly preferred support salt. Moreover, it is preferable to prepare the non-aqueous electrolyte so that the concentration of the supporting salt is within a range of 0.7 mol / L to 1.3 mol / L.
好適な一態様では、非水電解液に含まれる成分の中で、上記P−オキサラト化合物が最も高い還元電位(vs. Li/Li+)を示す。かかる組成とすることで、後述する充電処理においてP−オキサラト化合物を優先的に還元分解することができ、負極活物質の表面に該化合物由来の低抵抗な被膜を好適に形成することができる。 In a preferred embodiment, the P-oxalato compound exhibits the highest reduction potential (vs. Li / Li + ) among the components contained in the non-aqueous electrolyte. By setting it as this composition, a P-oxalato compound can be reduced and decomposed preferentially in the charging process described later, and a low-resistance film derived from the compound can be suitably formed on the surface of the negative electrode active material.
このようにして、ここで開示される非水電解液二次電池組立体を構築することができる。ここで開示される電池組立体は、電極体と非水電解液とを有している。そして、上記非水電解液には、P−オキサラト化合物が0.01g/Ah以上0.5g/Ah以下の割合で含まれる。また、上記電極体は、正極活物質を有する正極と、負極活物質を有する負極とを備えている。そして、上記正極活物質のDEP吸油量は25ml/100g以上48ml/100g以下である。 In this manner, the non-aqueous electrolyte secondary battery assembly disclosed herein can be constructed. The battery assembly disclosed here has an electrode body and a non-aqueous electrolyte. And in the said non-aqueous electrolyte, a P-oxalato compound is contained in the ratio of 0.01 g / Ah or more and 0.5 g / Ah or less. The electrode body includes a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material. And the DEP oil absorption of the said positive electrode active material is 25 ml / 100g or more and 48 ml / 100g or less.
<iii.充電処理工程(コンディショニング処理工程)>
次いで、充電処理工程では、上記電極体(非水電解液二次電池組立体)に対して少なくとも1回の充電処理を行う。典型的には、該組立体の正極(正極端子)と負極(負極端子)の間に外部電源を接続し、所定の電圧範囲まで充電(典型的には定電流充電)を行う。これによって、少なくともP−オキサラト化合物の一部が負極で還元分解され、負極活物質の表面にその分解物からなる被膜が形成される。
<Iii. Charging process (conditioning process)>
Next, in the charging process, at least one charging process is performed on the electrode body (nonaqueous electrolyte secondary battery assembly). Typically, an external power source is connected between the positive electrode (positive electrode terminal) and the negative electrode (negative electrode terminal) of the assembly, and charging (typically constant current charging) is performed to a predetermined voltage range. As a result, at least a part of the P-oxalato compound is reduced and decomposed at the negative electrode, and a film made of the decomposition product is formed on the surface of the negative electrode active material.
充電処理は、負極の電位(vs. Li/Li+)が、P−オキサラト化合物の少なくとも1種の還元電位(vs. Li/Li+)と概ね同等またはそれよりも0.05V(vs. Li/Li+)以上(好ましくは0.1V(vs. Li/Li+)以上)低くなるまで行うことが好ましい。これにより、負極活物質表面に低抵抗な被膜を安定的に形成することができる。充電方式は特に限定されず、例えば、上記負極の電位に到達するまで定電流で充電する方式(CC充電)で行ってもよく、上記負極の電位に到達するまで定電流で充電した後、定電圧で充電する方式(CCCV充電)により行ってもよい。CC充電時のレートは、例えば1/10C〜10C程度とすることができる。また、充電処理は1回でもよく、例えば放電処理を挟んで2回以上繰り返し行うこともできる。
このようにして、ここで開示される非水電解液二次電池を構築することができる。
Charging process, the negative electrode potential (vs. Li / Li +) is, P- oxalato least one reduction potential (vs. Li / Li +) and substantially equal to or greater even 0.05V compound (vs. Li / Li + ) or higher (preferably 0.1 V (vs. Li / Li + ) or higher). Thereby, a low-resistance film can be stably formed on the surface of the negative electrode active material. The charging method is not particularly limited. For example, charging may be performed with a constant current (CC charging) until reaching the potential of the negative electrode. After charging with a constant current until the potential of the negative electrode is reached, the charging method may be constant. You may carry out by the system (CCCV charge) charged with a voltage. The rate at the time of CC charging can be set to, for example, about 1 / 10C to 10C. Further, the charging process may be performed once, for example, it may be repeated twice or more with the discharging process interposed therebetween.
In this way, the non-aqueous electrolyte secondary battery disclosed herein can be constructed.
特に限定することを意図したものではないが、本発明の一実施形態に係る非水電解液二次電池の概略構成として、扁平に捲回された電極体(捲回電極体)と非水電解液とを扁平な直方体形状の容器(電池ケース)に収容した形態の非水電解液二次電池(単電池)を例として、本発明を詳細に説明する。以下の図面において、同じ作用を奏する部材・部位には同じ符号を付し、重複する説明は省略または簡略化することがある。各図における寸法関係(長さ、幅、厚さ等)は、必ずしも実際の寸法関係を反映するものではない。 Although not intended to be particularly limited, as a schematic configuration of the nonaqueous electrolyte secondary battery according to one embodiment of the present invention, a flatly wound electrode body (winding electrode body) and nonaqueous electrolysis The present invention will be described in detail by taking, as an example, a nonaqueous electrolyte secondary battery (unit cell) in a form in which a liquid is accommodated in a flat rectangular parallelepiped container (battery case). In the following drawings, members / parts having the same action are denoted by the same reference numerals, and redundant description may be omitted or simplified. The dimensional relationship (length, width, thickness, etc.) in each drawing does not necessarily reflect the actual dimensional relationship.
図1は、非水電解液二次電池100の断面構造を模式的に示す縦断面図である。非水電解液二次電池100は、長尺状の正極シート10と長尺状の負極シート20とが長尺状のセパレータシート40を介して扁平に捲回された形態の電極体(捲回電極体)80が、図示しない非水電解液とともに扁平な箱型形状の電池ケース50内に収容された構成を有する。なお、充電処理を施す前の非水電解液二次電池100は、非水電解液二次電池組立体である。
電池ケース50は、上端が開放された扁平な直方体形状(箱型)の電池ケース本体52と、その開口部を塞ぐ蓋体54とを備えている。電池ケース50の上面(すなわち蓋体54)には、捲回電極体80の正極と電気的に接続する外部接続用の正極端子70、および捲回電極体80の負極と電気的に接続する負極端子72が設けられている。蓋体54にはまた、従来の非水電解液二次電池の電池ケースと同様に、電池ケース50の内部で発生したガスをケース50の外部に排出するための安全弁55が備えられている。
FIG. 1 is a longitudinal sectional view schematically showing a sectional structure of a nonaqueous electrolyte
The
捲回電極体80は、組み立てる前段階において、長尺シート状の正極(正極シート)10と、長尺シート状の負極(負極シート)20とを備えている。正極シート10は、長尺状の正極集電体と、その少なくとも一方の表面(典型的には両面)に長手方向に沿って形成された正極活物質層14とを備えている。負極シート20は、長尺状の負極集電体と、その少なくとも一方の表面(典型的には両面)に長手方向に沿って形成された負極活物質層24とを備えている。また、正極活物質層14と負極活物質層24との間には、両者の直接接触を防ぐ絶縁層が配置されている。ここでは、上記絶縁層として2枚の長尺シート状のセパレータ40を使用している。このような捲回電極体80は、例えば、正極シート10、セパレータシート40、負極シート20、セパレータシート40の順に重ね合わせた積層体を長手方向に捲回し、得られた捲回体を側面方向から押圧して拉げさせることによって扁平形状に成形することにより作製することができる。
The
捲回電極体80の捲回軸方向の一の端部から他の一の端部に向かう方向として規定される幅方向において、その中央部分には、正極集電体の表面に形成された正極活物質層14と負極集電体の表面に形成された負極活物質層24とが重なり合って密に積層された捲回コア部分が形成されている。また、捲回電極体80の捲回軸方向の両端部では、正極シート10の正極活物質層非形成部および負極シート20の負極活物質層非形成部が、それぞれ捲回コア部分から外方にはみ出ている。そして、正極側はみ出し部分には正極集電板が、負極側はみ出し部分には負極集電板が、それぞれ付設され、正極端子70および上記負極端子72とそれぞれ電気的に接続されている。
A positive electrode formed on the surface of the positive electrode current collector in the width direction defined as a direction from one end portion of the
かかる構成の非水電解液二次電池100は、例えば、ケース50の開口部から電極体80を内部に収容し、該ケース50の開口部に蓋体54を取り付けた後、蓋体54に設けられた図示しない電解液注入孔から非水電解液を注入し、次いでかかる注入孔を塞ぐことによって構築することができる。
For example, the non-aqueous electrolyte
ここで開示される非水電解液二次電池は各種用途に利用可能であるが、P−オキサラト化合物添加の効果が好適に発揮され、耐久性とハイレート特性とを高いレベルで両立可能なことを特徴とする。したがって、このような性質を活かして、ハイブリッド自動車(HV)、プラグインハイブリッド自動車(PHV)、電気自動車(EV)等の車両に搭載される駆動用電源として好適に用いることができる。 The non-aqueous electrolyte secondary battery disclosed herein can be used for various applications, but the effect of adding a P-oxalato compound is suitably exhibited, and both durability and high-rate characteristics can be achieved at a high level. Features. Therefore, taking advantage of such properties, it can be suitably used as a driving power source mounted on a vehicle such as a hybrid vehicle (HV), a plug-in hybrid vehicle (PHV), or an electric vehicle (EV).
以下、本発明に関するいくつかの実施例を説明するが、本発明をかかる具体例に示すものに限定することを意図したものではない。 Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to the specific examples.
<リチウムイオン二次電池の作製>
先ず、正極活物質としてDEP吸油量の異なる8種類のLiNi1/3Co1/3Mn1/3O4粉末C1〜C8を用意し、これらの正極活物質を用いて正極を作製した。すなわち、この正極活物質と、導電材としてのアセチレンブラックと、バインダとしてのポリフッ化ビニリデンとを、これら材料の質量比が90:8:2となるようにN−メチルピロリドンと混合して、スラリー状の組成物を調製した。この組成物を厚さ15μmの長尺状アルミニウム箔(正極集電体)の両面に塗付して、乾燥後にプレスすることによって、正極集電体上に正極活物質層を有する正極シートC1〜C8(総厚み:75μm、電極密度:2.4g/cm3、長さ3500mm)を作製した。
<Production of lithium ion secondary battery>
First, eight types of LiNi 1/3 Co 1/3 Mn 1/3 O 4 powders C1 to C8 having different DEP oil absorption amounts were prepared as positive electrode active materials, and positive electrodes were produced using these positive electrode active materials. That is, this positive electrode active material, acetylene black as a conductive material, and polyvinylidene fluoride as a binder are mixed with N-methylpyrrolidone so that the mass ratio of these materials is 90: 8: 2, A shaped composition was prepared. This composition is applied to both sides of a 15 μm-thick long aluminum foil (positive electrode current collector) and dried and then pressed, whereby positive electrode sheets C1 to C1 having a positive electrode active material layer on the positive electrode current collector C8 (total thickness: 75 μm, electrode density: 2.4 g / cm 3 , length 3500 mm) was produced.
次に、負極活物質としての黒鉛粉末と、バインダとしてのスチレンブタジエンゴムと、分散剤としてのカルボキシメチルセルロースとを、これら材料の質量比が98:1:1となるようにイオン交換水と混合して、スラリー状の組成物を調製した。この組成物を厚さ10μmの銅箔(負極集電体)の両面に塗付して、乾燥後にプレスすることによって、負極集電体上に負極活物質層を有する負極シート(総厚み:85μm、電極密度:1.2g/cm3、長さ3700mm)を作製した。 Next, graphite powder as a negative electrode active material, styrene butadiene rubber as a binder, and carboxymethyl cellulose as a dispersant are mixed with ion-exchanged water so that the mass ratio of these materials is 98: 1: 1. Thus, a slurry-like composition was prepared. A negative electrode sheet having a negative electrode active material layer on the negative electrode current collector (total thickness: 85 μm) by applying this composition to both sides of a copper foil (negative electrode current collector) having a thickness of 10 μm and pressing after drying. Electrode density: 1.2 g / cm 3 , length 3700 mm).
次に、上記作製した正極シートC1〜C8のそれぞれを、2枚のセパレータシートを介して上記作製した負極シートと積層した。セパレータシートとしては、ポリエチレン(PE)の両面にポリプロピレン(PP)が積層された三層構造のものを用いた。この積層体を長尺方向に捲回した後、扁平形状に成形することで、正極シートC1〜C8に対応する計8種類の捲回電極体を作製した。
次に、電池ケースの蓋体に正極端子および負極端子を取り付け、これらの端子を、捲回電極体端部に露出した正極集電体および負極集電体にそれぞれ溶接した。このようにして蓋体と連結された捲回電極体を電池ケースの開口部からその内部に収容し、開口部と蓋体を溶接した。
Next, each of the produced positive electrode sheets C1 to C8 was laminated with the produced negative electrode sheet via two separator sheets. As the separator sheet, a three-layer structure in which polypropylene (PP) was laminated on both sides of polyethylene (PE) was used. After winding this laminated body in the longitudinal direction, a total of eight types of wound electrode bodies corresponding to the positive electrode sheets C1 to C8 were produced by forming into a flat shape.
Next, the positive electrode terminal and the negative electrode terminal were attached to the lid of the battery case, and these terminals were welded to the positive electrode current collector and the negative electrode current collector exposed at the ends of the wound electrode body, respectively. The wound electrode body thus connected to the lid body was accommodated in the battery case through the opening thereof, and the opening and the lid body were welded.
次に、リチウムジフルオロビス(オキサラト)ホスフェート(LPFO)の割合が異なる9種類の非水電解液を調製した。すなわち、エチレンカーボネート(EC)とジメチルカーボネート(DMC)とエチルメチルカーボネート(EMC)とをEC:DMC:EMC=30:40:30の体積比で含む混合溶媒に、支持塩としてのLiPF6を1.1mol/Lの濃度で溶解させたものと、これに加えて、表1に示す割合(モル/L)で非水電解液中にリチウムジフルオロビス(オキサラト)ホスフェートを含ませもの(8種類)とをそれぞれ調製した。なお、ここで使用したリチウムジフルオロビス(オキサラト)ホスフェートには、2モル%〜3モル%程度の割合でリチウムテトラフルオロ(オキサラト)ホスフェートが含まれていた。
そして、上記電池ケースの蓋体に設けられた電解液注入孔から非水電解液を注入して、リチウムイオン二次電池を構築した。ここでは、上記8種類の捲回電極体と上記9種類の非水電解液とをそれぞれ組み合わせて、計72種類のリチウムイオン二次電池を構築した。
Next, nine types of non-aqueous electrolytes with different lithium difluorobis (oxalato) phosphate (LPFO) ratios were prepared. That is, in a mixed solvent containing ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) in a volume ratio of EC: DMC: EMC = 30: 40: 30, LiPF 6 as a supporting salt is 1 .1 mol / L dissolved and in addition to this, non-aqueous electrolyte containing lithium difluorobis (oxalato) phosphate in the ratio (mol / L) shown in Table 1 (8 types) Were prepared respectively. The lithium difluorobis (oxalato) phosphate used here contained lithium tetrafluoro (oxalato) phosphate at a ratio of about 2 mol% to 3 mol%.
And the non-aqueous electrolyte was inject | poured from the electrolyte injection hole provided in the cover body of the said battery case, and the lithium ion secondary battery was constructed | assembled. Here, a total of 72 types of lithium ion secondary batteries were constructed by combining the 8 types of wound electrode bodies and the 9 types of non-aqueous electrolytes, respectively.
(電池容量)
上記構築したリチウムイオン二次電池に対して、充電処理を行った。具体的には、25℃の環境下において、上記電池を正負極端子間の電圧が4.1Vになるまで1/3Cの定電流で充電(CC充電)し、続いて合計の充電時間が1.5時間となるまで定電圧で充電(CV充電)した後、10分間休止し、正負極端子間の電圧が3.0Vになるまで1/3Cの定電流で放電(CC放電)し、続いて合計の充電時間が1.5時間となるまで定電圧で放電(CV放電)した後、10分休止する操作を1サイクルとして、これを3サイクル繰り返した。この充電処理によって、負極活物質の表面にP−オキサラト化合物由来の(シュウ酸イオンを含む)被膜を形成した。そして、3サイクル目のCCCV放電容量を電池容量(初期容量)とした。また、上記LPFOの添加量(モル/L)を質量(g)に換算し、上記電池容量(Ah)で除すことによって、電池容量あたりのリチウムジフルオロビス(オキサラト)ホスフェートの添加量(g/Ah)を算出した。結果を表1に示す。
(Battery capacity)
The lithium ion secondary battery constructed as described above was charged. Specifically, in an environment of 25 ° C., the battery is charged with a constant current of 1/3 C (CC charge) until the voltage between the positive and negative terminals becomes 4.1 V, and then the total charging time is 1 Charge at a constant voltage (CV charge) until 5 hours, then rest for 10 minutes, discharge at a constant current of 1/3 C (CC discharge) until the voltage between the positive and negative terminals reaches 3.0 V, then Then, after discharging at a constant voltage (CV discharge) until the total charging time became 1.5 hours, an operation of resting for 10 minutes was defined as 1 cycle, and this was repeated 3 cycles. By this charging treatment, a film (including oxalate ions) derived from the P-oxalato compound was formed on the surface of the negative electrode active material. The CCCV discharge capacity at the third cycle was defined as the battery capacity (initial capacity). Further, the amount of LPFO added (mol / L) is converted to mass (g) and divided by the battery capacity (Ah), whereby the amount of lithium difluorobis (oxalato) phosphate added per battery capacity (g / Ah) was calculated. The results are shown in Table 1.
(反応抵抗)
次に、25℃の温度環境下において、上記電池を1Cの定電流充電によってSOC60%の充電状態に調整した。この電池について、−30℃の温度環境下で交流インピーダンス測定を行った。そして、得られたCole−Coleプロットの円弧部分の直径を反応抵抗(初期抵抗)として算出した。結果を表2および図2に示す。
(Reaction resistance)
Next, in a temperature environment of 25 ° C., the battery was adjusted to a SOC 60% charge state by 1 C constant current charging. This battery was subjected to AC impedance measurement under a temperature environment of −30 ° C. And the diameter of the circular arc part of the obtained Cole-Cole plot was computed as reaction resistance (initial resistance). The results are shown in Table 2 and FIG.
表2および図2から明らかなように、正極活物質のDEP吸油量に着目すると、DEP吸油量が大きくなるにしたがい反応抵抗は低下傾向を示したが、所定の量を超えると一転して増加傾向となった。この原因としては、DEP吸油量が大きくなるにつれて非水電解質との親和性が高まり反応抵抗が徐々に低減されるが、DEP吸油量があまりに大きくなりすぎると、正極近傍に存在する(例えば正極に吸着する)P−オキサラト化合物の分解生成物の量が増え、反応抵抗が増大することが考えられる。
また、LPFOの添加量についても同様の傾向がみられた。すなわち、当初はLPFOの添加量が増えるにしたがい反応抵抗は低下傾向を示したが、所定の添加量を超えると一転して増加傾向となった。この原因としては、LPFOの添加量が増えるにつれて負極活物質の表面に被膜が形成され、非水電解液の還元分解が抑制されるが、添加量があまりに多くなりすぎると、負極活物質の表面に過剰な被膜が形成されて電荷移動抵抗が増大することが考えられる。
このことから、正極活物質のDEP吸油量を25ml/100g以上48ml/100g以下(具体的には、28ml/100g以上48ml/100g以下)とし、且つ、LPFOの添加量を0.01g/Ah以上0.5g/Ah以下(具体的には、0.015g/Ah以上0.48g/Ah以下)とした場合に、従来に比べて反応抵抗を大幅に低減し得る(例えば90mΩ以下とし得る)ことがわかった。
As is apparent from Table 2 and FIG. 2, when attention is paid to the DEP oil absorption amount of the positive electrode active material, the reaction resistance showed a decreasing tendency as the DEP oil absorption amount increased, but when the amount exceeded the predetermined amount, the reaction resistance increased. It became a trend. The cause of this is that as the DEP oil absorption increases, the affinity with the non-aqueous electrolyte increases and the reaction resistance gradually decreases. However, if the DEP oil absorption becomes too large, it exists near the positive electrode (for example, in the positive electrode). It is conceivable that the amount of decomposition products of the P-oxalato compound (adsorbed) increases and the reaction resistance increases.
Moreover, the same tendency was seen also about the addition amount of LPFO. That is, initially, the reaction resistance tended to decrease as the amount of LPFO added increased, but when it exceeded the predetermined amount of addition, the reaction resistance tended to increase. The cause is that as the amount of LPFO added increases, a film is formed on the surface of the negative electrode active material, and the reductive decomposition of the non-aqueous electrolyte is suppressed, but if the amount added is too large, the surface of the negative electrode active material It is conceivable that an excessive film is formed on the surface and the charge transfer resistance is increased.
Therefore, the DEP oil absorption amount of the positive electrode active material is 25 ml / 100 g or more and 48 ml / 100 g or less (specifically, 28 ml / 100 g or more and 48 ml / 100 g or less), and the addition amount of LPFO is 0.01 g / Ah or more. When it is 0.5 g / Ah or less (specifically, 0.015 g / Ah or more and 0.48 g / Ah or less), the reaction resistance can be greatly reduced compared to the conventional case (for example, it can be 90 mΩ or less). I understood.
(放電ハイレートサイクル特性)
次に、25℃の温度環境下にて、上記電池をSOCが60%の状態に調整するために、まず1/3Cの定電流でCC充電し、さらに合計充電時間が2時間になるまでCV充電を行った。そして、同温度において、75Aの定電流で40秒間CC放電し、5秒間休止した後に、10Aの定電流で300秒間CC充電し、5秒間休止する操作を1サイクルとして、これを4000サイクル繰り返した。
試験終了後、上記初期抵抗と同様にして放電ハイレートサイクル試験後の反応抵抗を測定した。そして、放電ハイレートサイクル試験後の反応抵抗を初期の反応抵抗で除して、100を掛けることにより、反応抵抗増加率(%)を算出した。結果を、表3および図3に示す。
(Discharge high rate cycle characteristics)
Next, in order to adjust the battery to a state where the SOC is 60% under a temperature environment of 25 ° C., CC charging is first performed at a constant current of 1/3 C, and further CV until the total charging time becomes 2 hours. Charged. Then, at the same temperature, CC discharge was performed at a constant current of 75 A for 40 seconds, and after resting for 5 seconds, CC charging was performed for 300 seconds at a constant current of 10 A and resting for 5 seconds, and this was repeated 4000 cycles. .
After the test, the reaction resistance after the discharge high rate cycle test was measured in the same manner as the initial resistance. Then, the reaction resistance after the discharge high rate cycle test was divided by the initial reaction resistance and multiplied by 100 to calculate the reaction resistance increase rate (%). The results are shown in Table 3 and FIG.
表3および図3から明らかなように、正極活物質のDEP吸油量を30ml/100g以上48ml/100g以下(具体的には32ml/100g以上48ml/100g以下)とし、且つ、LPFOの添加量を0.01g/Ah以上0.4g/Ah以下(具体的には0.015g/Ah以上0.32g/Ah以下)とした場合に、放電ハイレートサイクル試験後の抵抗増加が大幅に減少した(例えば抵抗増加率が120%以下となった)。このことから、上記電池はハイレート放電に対して顕著に優れた耐久性を発揮し得ることがわかった。 As apparent from Table 3 and FIG. 3, the positive electrode active material has a DEP oil absorption of 30 ml / 100 g to 48 ml / 100 g (specifically, 32 ml / 100 g to 48 ml / 100 g), and the amount of LPFO added is In the case of 0.01 g / Ah or more and 0.4 g / Ah or less (specifically, 0.015 g / Ah or more and 0.32 g / Ah or less), the increase in resistance after the discharge high rate cycle test was significantly reduced (for example, Resistance increase rate became 120% or less). From this, it was found that the above-mentioned battery can exhibit remarkably excellent durability against high rate discharge.
以上、本発明を詳細に説明したが、上記実施形態および実施例は例示にすぎず、ここで開示される発明には上述の具体例を様々に変形、変更したものが含まれる。 As mentioned above, although this invention was demonstrated in detail, the said embodiment and Example are only illustrations and what changed and changed the above-mentioned specific example is contained in the invention disclosed here.
10 正極シート(正極)
14 正極活物質層
20 負極シート(負極)
24 負極活物質層
40 セパレータシート(セパレータ)
50 電池ケース
52 電池ケース本体
54 蓋体
55 安全弁
70 正極端子
72 負極端子
80 捲回電極体
100 非水電解液二次電池
10 Positive electrode sheet (positive electrode)
14 Positive electrode
24 Negative electrode
DESCRIPTION OF
Claims (6)
正極活物質を有する正極と、負極活物質を有する負極と、を備える電極体を準備すること;
前記電極体を非水電解液とともに電池ケース内に収容すること;および、
前記電極体に対して少なくとも1回の充電処理を行うこと;
を包含し、
ここで、前記正極活物質としては、DEP吸油量が25ml/100g以上48ml/100g以下のものを用い、且つ、
前記非水電解液には、以下の一般式(1):
A+[PX6−2n(C2O4)n]− (1)
(式(1)中において、A+はアルカリ金属のカチオンであり、Xはハロゲン原子であり、nは、1または2または3である。)
で示される化合物を、電池の容量1Ahあたり0.01g以上0.5g以下の割合で含ませることを特徴とする、非水電解液二次電池の製造方法。 A method of manufacturing a non-aqueous electrolyte secondary battery comprising:
Preparing an electrode body comprising a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material;
Containing the electrode body together with a non-aqueous electrolyte in a battery case; and
Performing at least one charging process on the electrode body;
Including
Here, a positive electrode active material having a DEP oil absorption of 25 ml / 100 g or more and 48 ml / 100 g or less, and
The non-aqueous electrolyte includes the following general formula (1):
A + [PX 6-2n (C 2 O 4 ) n ] − (1)
(In the formula (1), A + is an alkali metal cation, X is a halogen atom, and n is 1 or 2 or 3.)
The manufacturing method of the nonaqueous electrolyte secondary battery characterized by including the compound shown by these in the ratio of 0.01 g or more and 0.5 g or less per battery capacity 1Ah.
正極活物質を有する正極と、負極活物質を有する負極と、を備える電極体と、
非水電解液と、を有し、
ここで、前記正極活物質のDEP吸油量は25ml/100g以上48ml/100g以下であり、且つ、
前記非水電解液には、以下の一般式(1):
A+[PX6−2n(C2O4)n]− (1)
(式(1)中において、A+はアルカリ金属のカチオンであり、Xはハロゲン原子であり、nは、1または2または3である。)
で示される化合物が、電池の容量1Ahあたり0.01g以上0.5g以下の割合で含まれる、充電処理が施される前の電池組立体。 A non-aqueous electrolyte secondary battery assembly comprising:
An electrode body comprising a positive electrode having a positive electrode active material and a negative electrode having a negative electrode active material;
A non-aqueous electrolyte, and
Here, the DEP oil absorption amount of the positive electrode active material is 25 ml / 100 g or more and 48 ml / 100 g or less, and
The non-aqueous electrolyte includes the following general formula (1):
A + [PX 6-2n (C 2 O 4 ) n ] − (1)
(In the formula (1), A + is an alkali metal cation, X is a halogen atom, and n is 1 or 2 or 3.)
The battery assembly before being subjected to the charging treatment, in which the compound represented by is contained at a ratio of 0.01 g to 0.5 g per 1 Ah of the battery capacity.
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