JP6516541B2 - Non-aqueous electrolyte secondary battery and its assembled battery - Google Patents
Non-aqueous electrolyte secondary battery and its assembled battery Download PDFInfo
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- JP6516541B2 JP6516541B2 JP2015084517A JP2015084517A JP6516541B2 JP 6516541 B2 JP6516541 B2 JP 6516541B2 JP 2015084517 A JP2015084517 A JP 2015084517A JP 2015084517 A JP2015084517 A JP 2015084517A JP 6516541 B2 JP6516541 B2 JP 6516541B2
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- aqueous electrolyte
- negative electrode
- secondary battery
- positive electrode
- electrolyte secondary
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 70
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 229910006884 Li1+xMyMn2-x-yO4 Inorganic materials 0.000 claims 1
- 229910006878 Li1+xMyMn2−x−yO4 Inorganic materials 0.000 claims 1
- -1 halogen anion Chemical class 0.000 description 25
- 239000007789 gas Substances 0.000 description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000011888 foil Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000002482 conductive additive Substances 0.000 description 7
- 230000001629 suppression Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910009615 Li1.1Al0.1Mn1.8O4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910011458 Li4/3 Ti5/3O4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-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
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000005593 norbornanyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は非水電解液二次電池及びその組電池に関するものである。 The present invention relates to a non-aqueous electrolyte secondary battery and an assembled battery thereof.
近年、携帯機器、ハイブリット自動車、電気自動車、家庭用蓄電用途に用いられる非水電解質二次電池の研究開発が盛んに行われている。これらの分野に用いられる非水電解質二次電池は、正極活物質としてリチウム含有コバルト複合酸化物やリチウム含有ニッケル複合酸化物、負極活物質としてカーボン系材料、電解液としてＬｉＢＦ４、ＬｉＰＦ６等のリチウム塩を有機溶媒に溶解した非水電解質をそれぞれ用いており、高容量、高出力など複数の特性を同時に満たすための研究が継続して行われている。さらに近年では電池の発熱・発火現象が報告されており、これまでよりも高い安全性を有する電池の開発が求められている。 BACKGROUND ART In recent years, research and development of non-aqueous electrolyte secondary batteries used for portable devices, hybrid vehicles, electric vehicles, and household storage applications have been actively conducted. Non-aqueous electrolyte secondary batteries used in these fields include lithium-containing cobalt composite oxides and lithium-containing nickel composite oxides as positive electrode active materials, carbon-based materials as negative electrode active materials, LiBF 4 and LiPF 6 as electrolytes, etc. Non-aqueous electrolytes in which a lithium salt is dissolved in an organic solvent are used respectively, and researches for simultaneously satisfying a plurality of characteristics such as high capacity and high output are continuously conducted. Furthermore, in recent years, heat generation and ignition phenomena of batteries have been reported, and development of batteries having higher safety than before is required.
そのような特性を満たすものとして負極の集電箔に塗工される負極活物質に、チタン酸リチウムや二酸化チタンのようなチタン含有酸化物を用いた非水電解質二次電池が開発されている（例えば、特許文献１）。しかし、負極の活物質にチタン含有酸化物を用いた非水電解質二次電池は、充放電サイクル時に活物質表面の異常活性点が電解液を分解することによりガスが発生し、その結果、内圧のため電池が膨らみ、電池特性が低下するという問題がある。 Non-aqueous electrolyte secondary batteries have been developed that use titanium-containing oxides such as lithium titanate or titanium dioxide as the negative electrode active material to be coated on the current collector foil of the negative electrode as one that satisfies such characteristics. (For example, patent document 1). However, in a non-aqueous electrolyte secondary battery using a titanium-containing oxide as the active material of the negative electrode, the abnormal active point on the surface of the active material decomposes the electrolyte during charge and discharge cycles to generate gas, and as a result, the internal pressure As a result, there is a problem that the battery expands and the battery characteristics deteriorate.
特許文献２には、電池ケース内に非水電解液が供給されているリチウムイオン二次電池において、非水電解液に、シルセスキオキサンを含ませ、負極の近傍に、シルセスキオキサンおよび／またはその反応生成物を存在させることにより、充放電を繰り返した際の電池容量の低下を抑制することに関する記載がある。しかしながら、一般にシルセスキオキサン自体は有機溶媒への溶解度が低いため、添加量が多い場合、電解液に溶けていないシルセスキオキサンにより、特性劣化が引き起こされると考えられ、改善が必要である。 According to Patent Document 2, in a lithium ion secondary battery in which a non-aqueous electrolytic solution is supplied in a battery case, silsesquioxane is contained in the non-aqueous electrolytic solution, and silsesquioxane and There is a statement about suppressing the fall of the battery capacity at the time of repeating charge and discharge by making the reaction product exist. However, since silsesquioxane itself is generally low in solubility in organic solvents, it is considered that silsesquioxane not dissolved in the electrolytic solution causes property deterioration when the amount added is large, and improvement is necessary. .
本発明が解決しようとする課題は、負極活物質にチタン含有酸化物を用いた非水電解質二次電池において、サイクル運転時においてガス発生が少なく、優れたサイクル安定性を発現する非水電解質二次電池を提供することである。 The problem to be solved by the present invention is that, in a non-aqueous electrolyte secondary battery using a titanium-containing oxide as a negative electrode active material, a non-aqueous electrolyte 2 that exhibits excellent cycle stability with less gas generation during cycle operation It is to provide the following battery.
本発明者らが、上記課題を解決するために鋭意検討した結果、負極にチタン含有酸化物を用い、非水電解質にシルセスキオキサン構造を有する塩を添加することで、電極表面にイオン性の保護層が形成され、効率的なリチウムイオンの授受を可能としつつ、活物質表面の異常活性点による溶媒の分解に伴うガス発生を抑制することができ、出力特性・サイクル特性の両立が可能となることを見出し、本発明を完成するに至った。 As a result of intensive investigations by the present inventors to solve the above problems, it is possible to use the titanium-containing oxide for the negative electrode and add a salt having a silsesquioxane structure to the non-aqueous electrolyte to make the electrode surface ionic. Is formed, which enables efficient lithium ion exchange while suppressing gas generation accompanying decomposition of the solvent due to the abnormal active point on the surface of the active material, enabling both output characteristics and cycle characteristics to be achieved. The present invention has been completed.
本発明は、非水電解質に添加するシルセスキオキサンがアニオンを包接している塩、及び／またはイオン性官能基を有する塩であるため、電解液への溶解性が高く、上記の保護膜形成が効果的に行われ、効率的にガス発生抑制や電池特性低下防止の効果が発現する。 In the present invention, since the silsesquioxane added to the non-aqueous electrolyte is a salt including an anion and / or a salt having an ionic functional group, the solubility in the electrolytic solution is high, and the protective film described above The formation is effectively performed, and the effects of suppressing gas generation and preventing deterioration of the battery characteristics are exhibited efficiently.
すなわち、本発明は、負極、正極、及び前記負極と前記正極との間に介在される非水電解質を備える二次電池であって、前記負極が、負極活物質としてチタン含有酸化物を含み、前記非水電解質が、シルセスキオキサン構造を有する塩を含有してなり、前記シルセスキオキサン構造を有する塩が、前記非水電解質１００重量％に対して０．０１重量％以上であることを特徴とする、非水電解質二次電池に関する。 That is, the present invention is a secondary battery comprising a negative electrode, a positive electrode, and a non-aqueous electrolyte interposed between the negative electrode and the positive electrode, wherein the negative electrode contains a titanium-containing oxide as a negative electrode active material, The non-aqueous electrolyte contains a salt having a silsesquioxane structure, and the salt having a silsesquioxane structure is 0.01% by weight or more based on 100% by weight of the non-aqueous electrolyte The present invention relates to a non-aqueous electrolyte secondary battery characterized by
また、前記シルセスキオキサン構造が、以下の式（１）で表すことのできることが好ましい。 Moreover, it is preferable that the said silsesquioxane structure can be represented by the following formula (1).
上記式中、Ｒは同一であっても、異なっていてもよく、いずれも水素原子または水素原子や炭素原子が他の元素で置換されていてもよい炭素原子数１〜１２の有機基であり、ｎは１〜１０の整数である。 In the above formulas, R may be the same or different, and each is a hydrogen atom or an organic group having 1 to 12 carbon atoms in which a hydrogen atom or a carbon atom may be substituted with another element, , N is an integer of 1 to 10.
また、前記シルセスキオキサン構造を有する塩が、かご型シルセスキオキサン構造を有することが好ましい。 The salt having a silsesquioxane structure preferably has a cage silsesquioxane structure.
また、前記シルセスキオキサン構造を有する塩が、分子内にハロゲンアニオンを包接していることが好ましい。 Moreover, it is preferable that the salt which has the said silsesquioxane structure has included the halogen anion in the molecule | numerator.
また、前記Ｒの少なくとも１つが重合性官能基及び／またはイオン性官能基を有していることが好ましい。 Moreover, it is preferable that at least one of the said R has a polymerizable functional group and / or an ionic functional group.
また、前記チタン含有酸化物が、チタン酸リチウムおよび／又は二酸化チタンであることが好ましい。 The titanium-containing oxide is preferably lithium titanate and / or titanium dioxide.
また、前記正極において、正極活物質がＬｉ１＋ｘＭｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．２、０＜ｙ≦０．６、Ｍは２〜１３族でかつ第３〜４周期に属する元素からなる群から選択される少なくとも１種）で表されるスピネル型マンガン酸リチウムを含むことが好ましい。 In the positive electrode, the positive electrode active material is Li 1 + x M y Mn 2-xy O 4 (0 ≦ x ≦ 0.2, 0 <y ≦ 0.6, M is a group 2 to 13, and It is preferable to include spinel-type lithium manganate represented by at least one selected from the group consisting of elements belonging to four cycles.
また、上記非水電解質二次電池を複数個接続してなる組電池に関する。 The present invention also relates to a battery assembly formed by connecting a plurality of the non-aqueous electrolyte secondary batteries.
本発明によれば、充放電サイクル時のガス発生がなく、優れたサイクル安定性を有する非水電解質二次電池が得られる。 According to the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery having excellent cycle stability without gas generation during charge and discharge cycles.
本発明の一実施形態について説明すると以下の通りであるが、本発明はこれに限定されるものではない。 One embodiment of the present invention will be described as follows, but the present invention is not limited thereto.
本発明の非水電解質二次電池は、負極、正極、セパレータ、非水電解質、および外装材からなるリチウムイオン電池とすることができる。この正極及び負極には各々、リチウムイオンの挿入及び脱離が可能な活物質を含む活物質層が形成されており、この挿入及び脱離により、本発明のリチウムイオン二次電池の充電及び放電が為される。 The non-aqueous electrolyte secondary battery of the present invention can be a lithium ion battery composed of a negative electrode, a positive electrode, a separator, a non-aqueous electrolyte, and an exterior material. An active material layer containing an active material capable of inserting and releasing lithium ions is formed on each of the positive electrode and the negative electrode, and charging and discharging of the lithium ion secondary battery of the present invention are formed by the insertion and removal. Is done.
＜１．負極＞
本発明の非水電解質二次電池に用いる負極は、金属製集電体の両面に、少なくとも負極活物質が含まれる負極活物質層が形成されている。負極活物質としてチタン含有酸化物を含む。チタン含有酸化物としては、チタン酸リチウム、および／又は二酸化チタンが好ましい。中でも、材料自身の安定性が高いことから、チタン酸リチウムがより好ましく、リチウムイオンの挿入・脱離の反応における活物質の膨張収縮が小さい点から、スピネル構造のチタン酸リチウムが特に好ましい。チタン酸リチウムには、たとえばＮｂなどのリチウム、チタン以外の元素が微量含まれていてもよい。
<1. Negative electrode>
In the negative electrode used in the non-aqueous electrolyte secondary battery of the present invention, a negative electrode active material layer containing at least a negative electrode active material is formed on both sides of a metal current collector. A titanium-containing oxide is included as a negative electrode active material. As a titanium containing oxide, lithium titanate and / or titanium dioxide are preferable. Among them, lithium titanate is more preferable because the stability of the material itself is high, and lithium titanate having a spinel structure is particularly preferable because expansion and contraction of the active material in the reaction of insertion and desorption of lithium ions is small. The lithium titanate may contain, for example, lithium such as Nb, and a trace amount of an element other than titanium.
また、二酸化チタンとしては、Ｂ型二酸化チタン、アナターゼ型二酸化チタン、ラムズデライト型二酸化チタン等が例示されるが、不可逆容量が小さいこと、およびサイクル安定性に優れることから、Ｂ型二酸化チタンが好ましい。 Examples of titanium dioxide include B-type titanium dioxide, anatase-type titanium dioxide, and ramsdellite-type titanium dioxide, but B-type titanium dioxide is preferable because of its small irreversible capacity and excellent cycle stability. .
チタン含有酸化物の表面は、導電性向上、あるいは安定性向上のため、炭素材料、金属酸化物、あるいは高分子等で覆われてもよい。 The surface of the titanium-containing oxide may be covered with a carbon material, a metal oxide, a polymer or the like in order to improve the conductivity or the stability.
チタン含有酸化物は１種類でもよいし、２種類以上組み合わせて用いてもよい。 The titanium-containing oxide may be used alone or in combination of two or more.
本発明に係る前記チタン含有酸化物の平均粒子径は、副反応の抑制の観点から１μｍ以上、２０μｍ以下のものを用いることができるが、サイクル特性の観点から２μｍ以上、１５μｍ以下が好ましく、より好ましくは、３μｍ以上、１０μｍ以下である。 The average particle diameter of the titanium-containing oxide according to the present invention can be 1 μm or more and 20 μm or less from the viewpoint of suppression of side reactions, but is preferably 2 μm or more and 15 μm or less from the viewpoint of cycle characteristics Preferably, it is 3 micrometers or more and 10 micrometers or less.
本発明に係る前記チタン含有酸化物の比表面積は、１ｍ２／ｇ以上、２５ｍ２／ｇ以下のものを用いることができるが、良好なサイクル特性を示すことから、１．５ｍ２／ｇ以上、２０ｍ２／ｇ以下が好ましく、副反応の抑制とのバランスから、２ｍ２／ｇ以上、１５ｍ２／ｇ以下がより好ましい。 Although the specific surface area of the titanium-containing oxide according to the present invention can be 1 m 2 / g or more and 25 m 2 / g or less, since it exhibits good cycle characteristics, it can be 1.5 m 2 / g or more 20 m 2 / g or less is preferable, and 2 m 2 / g or more and 15 m 2 / g or less is more preferable from the balance with suppression of side reaction.
本発明の負極には導電助剤を含有してもよく、導電助材としては、特に限定されないが、金属材料、炭素材料が好ましい。金属材料の場合は、銅、およびニッケルなど、炭素材料の場合は天然黒鉛、人造黒鉛、気相成長炭素繊維、カーボンナノチューブ、アセチレンブラック、ケッチェンブラック、およびファーネスブラックなどが挙げられる。これら導電助材は１種類でもよいし、２種類以上用いてもよい。本発明において、負極に含まれる導電助材の量は、負極活物質１００重量部に対して、好ましくは１重量部以上３０重量部以下、より好ましくは２重量部以上１５重量部以下である。上記範囲であれば、負極の導電性が確保される。また、後述のバインダーとの接着性が維持され、集電体との接着性を十分に得ることができる。 The negative electrode of the present invention may contain a conductive aid. The conductive aid is not particularly limited, but metal materials and carbon materials are preferable. In the case of metal materials, copper and nickel, and in the case of carbon materials, natural graphite, artificial graphite, vapor grown carbon fibers, carbon nanotubes, acetylene black, ketjen black, furnace black and the like can be mentioned. These conductive additives may be used alone or in combination of two or more. In the present invention, the amount of the conductive auxiliary contained in the negative electrode is preferably 1 to 30 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the negative electrode active material. Within the above range, the conductivity of the negative electrode is secured. Moreover, the adhesiveness with the below-mentioned binder is maintained, and adhesiveness with a collector can fully be obtained.
本発明の負極には、活物質を集電体に結着させるためバインダーを使用してよい。バインダーとしては、特に限定されないが、例えば、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）、スチレン−ブタジエンゴム、ポリイミドおよびそれらの誘導体からなる群から選ばれる少なくとも１種を用いることができる。バインダーは負極の作製しやすさから、非水溶媒または水に溶解、または分散されていることが好ましい。非水溶媒は、特に限定されないが、例えば、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、酢酸メチル、酢酸エチル、およびテトラヒドロフランなどを挙げることができる。これらに分散剤、増粘剤を加えてもよい。本発明において、負極に含まれるバインダーの量は、負極活物質１００重量部に対して、好ましくは１重量部以上３０重量部以下、より好ましくは２重量部以上１５重量部以下である。上記範囲であれば、負極活物質と導電助材との接着性が維持され、集電体との接着性を十分に得ることができる。 In the negative electrode of the present invention, a binder may be used to bind the active material to the current collector. The binder is not particularly limited, and for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimide and derivatives thereof can be used. . The binder is preferably dissolved or dispersed in a non-aqueous solvent or water for the ease of preparation of the negative electrode. The non-aqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran. You may add a dispersing agent and a thickener to these. In the present invention, the amount of the binder contained in the negative electrode is preferably 1 to 30 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the negative electrode active material. If it is the said range, the adhesiveness of a negative electrode active material and a conductive support material will be maintained, and adhesiveness with a collector can fully be obtained.
本発明の負極は、負極活物質、導電助材、およびバインダーの混合物を集電体上に形成することによって作製されるが、作製方法の容易さから、上記混合物および溶媒でスラリーを作製し、得られたスラリーを集電体上に塗工した後に、溶媒を除去することによって作製する方法が好ましい。 The negative electrode of the present invention is produced by forming a mixture of a negative electrode active material, a conductive auxiliary and a binder on a current collector, but from the easiness of the production method, a slurry is produced with the above mixture and solvent, The method of producing by apply | coating the obtained slurry on a collector, and removing a solvent is preferable.
本発明の負極に用いることのできる集電体は、銅、ＳＵＳ、ニッケル、チタン、アルミニウムおよびそれらの合金が好ましい。集電体の厚みは、特に限定されないが、１０μｍ以上１００μｍ以下であることが好ましい。なお、集電体は、金属材料（銅、ＳＵＳ、ニッケル、チタン、およびそれらの合金）の表面に負極の電位で反応しない金属を被覆したものも用いることもできる。 The current collector that can be used for the negative electrode of the present invention is preferably copper, SUS, nickel, titanium, aluminum and their alloys. The thickness of the current collector is not particularly limited, but is preferably 10 μm or more and 100 μm or less. As the current collector, one obtained by coating the surface of a metal material (copper, SUS, nickel, titanium, and their alloys) with a metal that does not react at the potential of the negative electrode can also be used.
本発明において、負極の厚みは、特に限定されないが、１０μｍ以上２００μｍ以下であることが好ましい。 In the present invention, the thickness of the negative electrode is not particularly limited, but is preferably 10 μm or more and 200 μm or less.
本発明において、負極の密度は、１．０ｇ／ｃｍ３以上３．０ｇ／ｃｍ３以下であることが好ましく、負極活物質、導電助材との接触が十分にあり、かつ後述の非水電解質が負極内に浸透しやすいことから、１．３ｇ／ｃｍ３以上、２．７ｇ／ｃｍ３以下がさらに好ましく、負極活物質、導電助材との接触と、非水電解質の負極内へ浸透しやすさのバランスが最も取れている、１．５ｇ／ｃｍ３以上、２．５ｇ／ｃｍ３以下が特に好ましい。 In the present invention, the density of the negative electrode is preferably 1.0 g / cm 3 or more and 3.0 g / cm 3 or less, and there is sufficient contact with the negative electrode active material and the conductive additive, and the non-aqueous electrolyte described later Is more preferably 1.3 g / cm 3 or more and 2.7 g / cm 3 or less, because it is in contact with the negative electrode active material and the conductive additive, and penetrates into the negative electrode of the non-aqueous electrolyte. Particularly preferred is 1.5 g / cm 3 or more and 2.5 g / cm 3 or less, in which the easiness is well balanced.
前記負極の密度は、所望の厚みまで電極を圧縮することによって制御することが出来る。前記圧縮は、特に限定されないが、例えば、ロールプレス、油圧プレス等を用いて行うことができる。電極の圧縮は、後述の正極を形成する前でも、後でもよい。 The density of the negative electrode can be controlled by compressing the electrode to the desired thickness. Although the said compression is not specifically limited, For example, it can carry out using a roll press, a hydraulic press, etc. The compression of the electrode may be performed before or after forming the positive electrode described later.
前記負極の密度は、負極活物質層の厚みおよび重量から算出することが出来る。 The density of the negative electrode can be calculated from the thickness and weight of the negative electrode active material layer.
＜２．正極＞
本発明の非水電解質二次電池に用いる正極は、金属製集電体の両面に、少なくとも正極活物質が含まれる正極活物質層が形成されている。正極活物質としては特に限定されず、金属酸化物やリチウム遷移金属複合酸化物などが用いられ得る。これらの中で、良好なサイクル特性を示すことから、Ｌｉ１＋ｘＭｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．２、０＜ｙ≦０．６、Ｍは２〜１３族でかつ第３〜４周期に属する元素からなる群から選択される少なくとも１種）で表されるスピネル型マンガン酸リチウムが好ましい。前記Ｌｉ１＋ｘＭｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．２、０＜ｙ≦０．６、Ｍは２〜１３族でかつ第３〜４周期に属する元素からなる群から選択される少なくとも１種）で表されるスピネル型マンガン酸リチウムは、正極活物質自身の安定性向上の効果が大きい点から、２〜１３族でかつ第３〜４周期に属する元素は、Ａｌ、Ｍｇ、Ｚｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ｔｉ、Ｃｕ、Ｚｒ、およびＣｒが好ましく、Ａｌ、Ｍｇ、Ｚｎ、Ｎｉ、ＴｉおよびＣｒがより好ましく、正極活物質自身の安定性向上の効果が特に大きいことから、Ａｌ、Ｍｇ、Ｚｎ、ＴｉおよびＮｉが特に好ましい。
<2. Positive electrode>
In the positive electrode used in the non-aqueous electrolyte secondary battery of the present invention, a positive electrode active material layer containing at least a positive electrode active material is formed on both sides of a metal current collector. It does not specifically limit as a positive electrode active material, A metal oxide, lithium transition metal complex oxide, etc. may be used. Among these, Li 1 + x M y M n 2-x-y O 4 (0 ≦ x ≦ 0.2, 0 <y ≦ 0.6, and M is a group 2 to 13 because it exhibits good cycle characteristics. The spinel lithium manganate represented by at least one selected from the group consisting of the elements belonging to the third and fourth cycles is preferable. From the group consisting of the above-mentioned Li 1 + x M y Mn 2-xy O 4 (0 ≦ x ≦ 0.2, 0 <y ≦ 0.6, M is a group 2 to 13 and belongs to the third to fourth periods The spinel-type lithium manganate represented by at least one selected) has a large effect of improving the stability of the positive electrode active material itself, so that the element belonging to Groups 2 to 13 and the third to fourth cycles is Al Mg, Zn, Ni, Co, Fe, Ti, Cu, Zr, and Cr are preferable, Al, Mg, Zn, Ni, Ti, and Cr are more preferable, and the effect of improving the stability of the positive electrode active material itself is particularly large. Therefore, Al, Mg, Zn, Ti and Ni are particularly preferable.
これらの中でも、後述の非水電解質との組み合わせで、ガス発生減少、および充電終止電圧の高電圧化の効果が大きいことから、Ｌｉ１＋ｘＡｌｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）、Ｌｉ１＋ｘＭｇｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）、Ｌｉ１＋ｘＺｎｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）、Ｌｉ１＋ｘＣｒｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）Ｌｉ１＋ｘＮｉｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．０５、０．４５≦ｙ≦０．５）、Ｌｉ１＋ｘＮｉｙ−ｚＡｌｚＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．０５、０．４５≦ｙ≦０．５、０．００５≦ｚ≦０．０３）、およびＬｉ１＋ｘＮｉｙ−ｚＴｉｚＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．０５、０．４５≦ｙ≦０．５、０．００５≦ｚ≦０．０３）から選ばれる１種が好ましく、より大きい効果が得られる、Ｌｉ１＋ｘＡｌｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）、Ｌｉ１＋ｘＭｇｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．１、０＜ｙ≦０．１）、Ｌｉ１＋ｘＮｉｙＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．０５、０．４５≦ｙ≦０．５）、およびＬｉ１＋ｘＮｉｙ−ｚＴｉｚＭｎ２―ｘ―ｙＯ４（０≦ｘ≦０．０５、０．４５≦ｙ≦０．５、０．００５≦ｚ≦０．０３）が特に好ましい。 Among these, in combination with the non-aqueous electrolyte will be described later, the gas generation decreases, and since the effect of the higher voltage of the charge voltage is high, Li 1 + x Al y Mn 2-x-y O 4 (0 ≦ x ≦ 0.1, 0 <y ≦ 0.1), Li 1 + x Mg y Mn 2-xy O 4 (0 ≦ x ≦ 0.1, 0 <y ≦ 0.1), Li 1 + x Zn y Mn 2- xy O 4 (0 ≦ x ≦ 0.1, 0 <y ≦ 0.1), Li 1 + x Cr y Mn 2-xy O 4 (0 ≦ x ≦ 0.1, 0 <y ≦ 0. 1) Li 1 + x Ni y Mn 2-xy O 4 (0 ≦ x ≦ 0.05, 0.45 ≦ y ≦ 0.5), Li 1 + x Ni yz Al z Mn 2-xy O 4 (0 ≦ x ≦ 0.05,0.45 ≦ y ≦ 0.5,0.005 ≦ z ≦ 0.03), and Li 1 + x Ni y-z Ti z Mn 2-x Preferably one selected from y O 4 (0 ≦ x ≦ 0.05,0.45 ≦ y ≦ 0.5,0.005 ≦ z ≦ 0.03), greater effect can be obtained, Li 1 + x Al y Mn 2-xy O 4 (0 ≦ x ≦ 0.1, 0 <y ≦ 0.1), Li 1 + x Mg y Mn 2-xy O 4 (0 ≦ x ≦ 0.1, 0 <0 y ≦ 0.1), Li 1 + x Ni y Mn 2-xy O 4 (0 ≦ x ≦ 0.05, 0.45 ≦ y ≦ 0.5), and Li 1 + x Ni yz Ti z Mn 2 Particularly preferred is —xy O 4 (0 ≦ x ≦ 0.05, 0.45 ≦ y ≦ 0.5, 0.005 ≦ z ≦ 0.03).
これらの中から、負極活物質との組み合わせを考慮して適宜選択すればよい。また、複数の正極活物質を組み合わせて用いてもよい。 From among these, it may be appropriately selected in consideration of the combination with the negative electrode active material. Further, a plurality of positive electrode active materials may be used in combination.
本発明に用いられる正極活物質の表面は、導電性向上、あるいは安定性向上のため、炭素材料、金属酸化物、あるいは高分子等で覆われてもよい。 The surface of the positive electrode active material used in the present invention may be covered with a carbon material, a metal oxide, a polymer or the like in order to improve the conductivity or the stability.
本発明の正極には導電助材を含有させてもよい。導電助材としては、特に限定されないが、炭素材料が好ましい。例えば、天然黒鉛、人造黒鉛、気相成長炭素繊維、カーボンナノチューブ、アセチレンブラック、ケッチェンブラック、およびファーネスブラックなどが挙げられる。これら炭素材料は１種類でもよいし、２種類以上用いてもよい。本発明の正極に含まれる導電助材の量は、正極活物質１００重量部に対して、好ましくは１重量部以上３０重量部以下、より好ましくは２重量部以上１５重量部以下である。上記範囲であれば、正極の導電性が確保される。また、後述のバインダーとの接着性が維持され、集電体との接着性を十分に得ることができる。 The positive electrode of the present invention may contain a conductive aid. The conductive aid is not particularly limited, but a carbon material is preferable. Examples include natural graphite, artificial graphite, vapor grown carbon fibers, carbon nanotubes, acetylene black, ketjen black, and furnace black. These carbon materials may be used alone or in combination of two or more. The amount of the conductive auxiliary contained in the positive electrode of the present invention is preferably 1 to 30 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the positive electrode active material. If it is the said range, the electroconductivity of a positive electrode will be ensured. Moreover, the adhesiveness with the below-mentioned binder is maintained, and adhesiveness with a collector can fully be obtained.
本発明の正極にはバインダーを含有させてよい。バインダーは、特に限定されないが、例えば、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）、スチレン−ブタジエンゴム、ポリイミド、およびそれらの誘導体からなる群から選ばれる少なくとも１種を用いることができる。バインダーは正極の作製しやすさから、非水溶媒または水に溶解または分散されていることが好ましい。非水溶媒は、特に限定されないが、例えば、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、酢酸メチル、酢酸エチル、およびテトラヒドロフランなどを挙げることができる。これらに分散剤、増粘剤を加えてもよい。本発明の正極に含まれるバインダーの量は、正極活物質１００重量部に対して、好ましくは１重量部以上３０重量部以下、より好ましくは２重量部以上１５重量部以下である。上記範囲であれば、正極活物質と導電助材との接着性が維持され、集電体との接着性を十分に得ることができる。 The positive electrode of the present invention may contain a binder. The binder is not particularly limited, and for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimide, and derivatives thereof can be used. . The binder is preferably dissolved or dispersed in a non-aqueous solvent or water, for the ease of preparation of the positive electrode. The non-aqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran. You may add a dispersing agent and a thickener to these. The amount of the binder contained in the positive electrode of the present invention is preferably 1 to 30 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the positive electrode active material. If it is the said range, the adhesiveness of a positive electrode active material and a conductive support material will be maintained, and adhesiveness with a collector can fully be obtained.
本発明の正極は、正極活物質、導電助材、およびバインダーの混合物を集電体上に形成することによって作製されるが、作製方法の容易さから、上記混合物および溶媒でスラリーを作製し、得られたスラリーを集電体上に塗工した後に、溶媒を除去することによって作製する方法が好ましい。スラリーの作製は従来公知の条件、方法を使用すればよい。また、塗工、溶媒除去についても従来公知の条件、方法を使用すればよい。 The positive electrode of the present invention is produced by forming a mixture of a positive electrode active material, a conductive additive and a binder on a current collector, but from the easiness of the production method, a slurry is produced with the above mixture and solvent, The method of producing by apply | coating the obtained slurry on a collector, and removing a solvent is preferable. The preparation of the slurry may be carried out using conventionally known conditions and methods. In addition, conditions and methods known in the art may be used for coating and solvent removal.
本発明の正極に用いる集電体は、アルミニウムおよびその合金であることが好ましい。前記アルミニウムは、正極反応雰囲気下で安定であることから、特に限定されないが、ＪＩＳ規格１０３０、１０５０、１０８５、１Ｎ９０、１Ｎ９９等に代表される高純度アルミニウムであることが好ましい。集電体の厚みは、特に限定されないが、１０μｍ以上１００μｍ以下であることが好ましい。なお、集電体は、アルミニウム以外の金属（銅、ＳＵＳ、ニッケル、チタン、およびそれらの合金）の表面にアルミニウムを被覆したものも用いることもできる。 The current collector used for the positive electrode of the present invention is preferably aluminum and an alloy thereof. The aluminum is not particularly limited because it is stable in a positive electrode reaction atmosphere, but is preferably high purity aluminum represented by JIS standards 1030, 1050, 1085, 1N90, 1N99 and the like. The thickness of the current collector is not particularly limited, but is preferably 10 μm or more and 100 μm or less. As the current collector, one obtained by coating a surface of a metal other than aluminum (copper, SUS, nickel, titanium, and their alloys) with aluminum can also be used.
本発明の正極の厚みは、特に限定されないが、１０μｍ以上２００μｍ以下であることが好ましい。 The thickness of the positive electrode of the present invention is not particularly limited, but is preferably 10 μm or more and 200 μm or less.
本発明の正極の密度は、１．０ｇ／ｃｍ３以上４．０ｇ／ｃｍ３以下であることが好ましく、正極活物質、導電助材との接触が十分にあり、かつ後述の非水電解質が正極内に浸透しやすいことから、１．５ｇ／ｃｍ３以上、３．５ｇ／ｃｍ３以下がさらに好ましく、正極活物質、導電助材との接触と、非水電解質の正極内への浸透しやすさのバランスが最も取れている、２．０ｇ／ｃｍ３以上、３．０ｇ／ｃｍ３以下が特に好ましい。 The density of the positive electrode of the present invention is preferably 1.0 g / cm 3 or more and 4.0 g / cm 3 or less, and contact with the positive electrode active material and the conductive additive is sufficient. 1.5 g / cm 3 or more and 3.5 g / cm 3 or less is more preferable because it easily penetrates into the positive electrode, and contact with the positive electrode active material and the conductive additive and the non-aqueous electrolyte penetrates into the positive electrode 2.0 g / cm 3 or more and 3.0 g / cm 3 or less are particularly preferable, in which the balance of ease is most achieved.
前記正極の密度は、所望の厚みまで電極を圧縮することによって制御することが出来る。前記圧縮は、特に限定されないが、例えば、ロールプレス、油圧プレス等を用いて行うことができる。電極の圧縮は、前述の負極を形成する前でも、後でもよい。 The density of the positive electrode can be controlled by compressing the electrode to the desired thickness. Although the said compression is not specifically limited, For example, it can carry out using a roll press, a hydraulic press, etc. The compression of the electrode may be before or after forming the negative electrode described above.
前記正極の密度は、正極活物質層の厚みおよび重量から算出することが出来る。 The density of the positive electrode can be calculated from the thickness and weight of the positive electrode active material layer.
＜３．セパレータ＞
本発明の非水電解質二次電池に用いるセパレータは、前述の正極と負極との間に設置され、絶縁性かつ後述の非水電解質を含むことが出来る構造であればよく、例えば、ナイロン、セルロース、ポリスルホン、ポリエチレン、ポリプロピレン、ポリブテン、ポリアクリロニトリル、ポリイミド、ポリアミド、ポリエチレンテレフタラート、及びそれらを２種類以上複合したものの織布、不織布、微多孔膜などが挙げられる。
<3. Separator>
The separator used in the non-aqueous electrolyte secondary battery of the present invention may be any structure having an insulating property and capable of containing a non-aqueous electrolyte described later, which is disposed between the above-described positive electrode and negative electrode. And polysulphone, polyethylene, polypropylene, polybutene, polyacrylonitrile, polyimide, polyamide, polyethylene terephthalate, and a woven fabric, a non-woven fabric, and a microporous film of a composite of two or more of them.
セパレータには、各種可塑剤、酸化防止剤、難燃剤が含まれてもよいし、金属酸化物等で被覆されていてもよい。 The separator may contain various plasticizers, antioxidants, flame retardants, or may be coated with a metal oxide or the like.
セパレータの厚みは、特に限定されないが、１０μｍ以上１００μｍ以下であることが好ましく、１５μｍ以上５０μｍ以下であることがさらに好ましい。 The thickness of the separator is not particularly limited, but is preferably 10 μm or more and 100 μm or less, and more preferably 15 μm or more and 50 μm or less.
前記セパレータの空隙率は、３０％以上、９０％以下であることが好ましく、リチウムイオンの拡散性の確保、および短絡の防止のバランスの観点から、３５％以上、８５％以下がより好ましく、前記バランスが特に優れていることから、４０％以上、８０％以下が特に好ましい。 The porosity of the separator is preferably 30% or more and 90% or less, more preferably 35% or more and 85% or less from the viewpoint of balance between securing of lithium ion diffusion and prevention of short circuit, 40% or more and 80% or less are particularly preferable because the balance is particularly excellent.
＜４．非水電解質＞
本発明の非水電解質二次電池に用いる非水電解質は、前記負極と前記正極との間に介在され、それらの間のイオン伝達を媒介する働きを有する。
<4. Nonaqueous electrolyte>
The non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention is interposed between the negative electrode and the positive electrode and has a function of mediating ion transfer therebetween.
前記非水電解質は、シルセスキオキサン構造を有する塩を非水電解質１００重量％に対して０．０１重量％以上含有している。これにより、電極表面にイオン性の保護層が形成され、効率的なリチウムイオンの授受を可能としつつ、活物質表面の異常活性点による溶媒の分解に伴うガス発生を抑制することができ、出力特性・サイクル特性の両立が可能となる。 The non-aqueous electrolyte contains 0.01% by weight or more of a salt having a silsesquioxane structure with respect to 100% by weight of the non-aqueous electrolyte. As a result, an ionic protective layer is formed on the surface of the electrode, enabling efficient transfer of lithium ions, while suppressing gas generation accompanying decomposition of the solvent due to the abnormal active point on the surface of the active material. It is possible to achieve both characteristics and cycle characteristics.
非水電解質に用いられる、非水溶媒は、環状の非プロトン性溶媒及び／又は鎖状の非プロトン性溶媒を含むことが好ましい。環状の非プロトン性溶媒としては、環状カーボネート、環状エステル、環状スルホン及び環状エーテルなどが例示される。鎖状の非プロトン性溶媒としては、鎖状カーボネート、鎖状カルボン酸エステル及び鎖状エーテルなどが例示される。また、前記に加えアセトニトリルなどの一般的に非水電解質の溶媒として用いられる溶媒を用いても良い。より具体的には、ジメチルカーボネート、メチルエチルカーボネート、ジメチルカーボネート、ジプロピルカーボネート、メチルプロピルカーボネート、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、γ−ブチルラクトン、１，２−ジメトキシエタン、スルホラン、ジオキソラン、プロピオン酸メチルなどを用いることができる。これら溶媒は１種類で用いてもよいし、２種類以上混合しても用いてもよい。 The non-aqueous solvent used for the non-aqueous electrolyte preferably contains a cyclic aprotic solvent and / or a linear aprotic solvent. Examples of cyclic aprotic solvents include cyclic carbonates, cyclic esters, cyclic sulfones and cyclic ethers. Examples of linear aprotic solvents include linear carbonates, linear carboxylic acid esters and linear ethers. In addition to the above, a solvent generally used as a solvent for non-aqueous electrolyte such as acetonitrile may be used. More specifically, dimethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyl lactone, 1,2-dimethoxyethane, sulfolane, dioxolane, propione Methyl acid can be used. These solvents may be used alone or in combination of two or more.
非水電解質に用いるリチウム塩としてはＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＢＯＢ（Ｌｉｔｈｉｕｍ Ｂｉｓ （Ｏｘａｌａｔｏ） Ｂｏｒａｔｅ）、Ｌｉ[Ｎ（ＳＯ２ＣＦ３）２]、Ｌｉ[Ｎ（ＳＯ２Ｃ２Ｆ５）２]、Ｌｉ[Ｎ（ＳＯ２Ｆ）２]、Ｌｉ[Ｎ（ＣＮ）２]などが挙げられる。溶解度が高く、サイクル特性が良好なことから、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６、Ｌｉ[Ｎ（ＳＯ２Ｆ）２]、Ｌｉ[Ｎ（ＣＮ）２]、が好ましい。 Examples of lithium salts used for the non-aqueous electrolyte include LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBOB (Lithium Bis (Oxalato) Borate), Li [N (SO 2 CF 3 ) 2 ], Li [ N (SO 2 C 2 F 5 ) 2], Li [N (SO 2 F) 2], Li [N (CN) 2] , and the like. LiClO 4 , LiBF 4 , LiPF 6 , Li [N (SO 2 F) 2 ] and Li [N (CN) 2 ] are preferable because of high solubility and good cycle characteristics.
前記リチウム塩の濃度としては、０．５ｍｏｌ／Ｌ以上２．０ｍｏｌ／Ｌ以下であることが好ましい。 The concentration of the lithium salt is preferably 0.5 mol / L or more and 2.0 mol / L or less.
前記シルセスキオキサン構造は以下の式（１）で表される。 The silsesquioxane structure is represented by the following formula (1).
上記式中、Ｒは同一であっても、異なっていてもよく、いずれも水素原子または水素原子や炭素原子が他の元素で置換されていてもよい炭素原子数１〜１２の有機基であり、ｎは１〜１０の整数である。 In the above formulas, R may be the same or different, and each is a hydrogen atom or an organic group having 1 to 12 carbon atoms in which a hydrogen atom or a carbon atom may be substituted with another element, , N is an integer of 1 to 10.
上記式（１）中、Ｒとしては、水素原子；メチル基やエチル基などのアルキル基；ビニル基やアリル基などのアルケニル基；エチニル基やプロピニル基などのアルキニル基；シクロヘキシル基やノルボルナニル基などのシクロアルキル基；アルキル基を有していても良いフェニル基などのアリール基；トリメチルシリル基などのトリアルキルシリル基；トリメチルシロキシ基などのトリアルキルシロキシ基；これらの官能基の炭素原子に結合した水素原子の一部又は全部をハロゲン原子、シアノ基などで置換した、クロロメチル基、トリフルオロプロピル基、シアノエチル基、トリフルオロメチルフェニル基などが挙げられる。ガス抑制の観点からＲの少なくとも１つは重合性官能基であることが好ましい。これらの官能基の炭素数は、溶解性の観点から２〜８が好ましい。前記Ｒ中の重合性官能基としては、ビニル基、アリル基、スチリル基、アクリロイル基などが挙げられる。サイクル特性の観点からビニル基、アリル基が好ましく、ガス抑制の観点からビニル基が特に好ましい。 In the above formula (1), R represents a hydrogen atom; an alkyl group such as methyl or ethyl; an alkenyl group such as vinyl or allyl; an alkynyl such as ethynyl or propynyl; cyclohexyl or norbornanyl Cycloalkyl group; aryl group such as phenyl group which may have alkyl group; trialkylsilyl group such as trimethylsilyl group; trialkylsiloxy group such as trimethylsiloxy group; bonded to carbon atom of these functional groups A chloromethyl group, a trifluoropropyl group, a cyanoethyl group, a trifluoromethyl phenyl group etc. which substituted some or all of hydrogen atoms by the halogen atom, the cyano group etc. are mentioned. From the viewpoint of gas suppression, at least one of R is preferably a polymerizable functional group. The carbon number of these functional groups is preferably 2 to 8 from the viewpoint of solubility. As a polymerizable functional group in said R, a vinyl group, an allyl group, a styryl group, an acryloyl group etc. are mentioned. Vinyl groups and allyl groups are preferable from the viewpoint of cycle characteristics, and vinyl groups are particularly preferable from the viewpoint of gas suppression.
また、上記式中のｎはサイクル特性の観点から２〜８が好ましく、ガス抑制の観点から４または５が特に好ましい。 Further, n in the above formula is preferably 2 to 8 from the viewpoint of cycle characteristics, and particularly preferably 4 or 5 from the viewpoint of gas suppression.
シルセスキオキサン構造は特に限定されず、かご型、ラダー型、ランダム型のいずれであっても良く、２種類以上の混合物でもよい。中でも、サイクル特性の観点からかご型またはラダー型が好ましく、ガス抑制の観点からかご型が特に好ましい。 The silsesquioxane structure is not particularly limited, and may be a cage type, a ladder type, a random type, or a mixture of two or more. Among them, a cage type or a ladder type is preferable from the viewpoint of cycle characteristics, and a cage type is particularly preferable from the viewpoint of gas suppression.
ｎ＝４のかご型シルセスキオキサン（Ｔ８）としては以下の式（２）で表される。 As cage silsesquioxane (T8) of n = 4, it represents with following formula (2).
また、ｎ＝５のかご型シルセスキオキサン（Ｔ１０）としては以下の式（３）で表される。 Moreover, as cage silsesquioxane (T10) of n = 5, it represents with following formula (3).
前記シルセスキオキサン構造を有する塩は、分子内にアニオンを包接していることが好ましい。包接されるアニオンとしては、特に限定されないが、包接状態の安定性の観点からハロゲン化物イオンが好ましく、性能のバランスが良いことからフッ化物イオンが特に好ましい。前記シルセスキオキサン構造を有する塩が分子内にアニオンを包接している場合は、対カチオンを有するが、特に限定されず、アルカリ金属イオン、アルカリ土類金属イオン、テトラアルキルアンモニウムイオンやテトラアルキルホスホニウムイオン、イミダゾリウムイオンなどが挙げられる。出力特性や溶解性の観点から、リチウムイオン、ナトリウムイオン、マグネシウムイオン、テトラアルキルアンモニウムイオン、イミダゾリウムイオンが好ましい。テトラアルキルアンモニウムイオンやテトラアルキルホスホニウムイオン、イミダゾリウムイオンについては前記Ｒ中に含まれていても良い。 The salt having a silsesquioxane structure preferably includes an anion in the molecule. The anion to be included is not particularly limited, but halide ions are preferable from the viewpoint of stability of the inclusion state, and fluoride ions are particularly preferable because they have a good balance of performance. When the salt having a silsesquioxane structure includes an anion in the molecule, it has a counter cation, but is not particularly limited, and alkali metal ions, alkaline earth metal ions, tetraalkyl ammonium ions, tetra alkyl A phosphonium ion, an imidazolium ion, etc. are mentioned. From the viewpoint of output characteristics and solubility, lithium ion, sodium ion, magnesium ion, tetraalkylammonium ion and imidazolium ion are preferable. The tetraalkyl ammonium ion, the tetraalkyl phosphonium ion, and the imidazolium ion may be contained in the above-mentioned R.
前記シルセスキオキサン構造を有する塩が分子内にアニオンを包接していない場合は、前記Ｒの少なくとも１つがイオン性官能基を有している。 When the salt having a silsesquioxane structure does not clathrate an anion in the molecule, at least one of the Rs has an ionic functional group.
前記Ｒ中のイオン性官能基としては、カチオン性のテトラアルキルアンモニウム基、イミダゾリウム基、テトラアルキルホスホニウム基；アニオン性のホスフェート基、カルボキシレート基、ナイトレート基などが挙げられる。サイクル特性の観点からカチオン性の官能基が好ましく、ガス抑制の観点からテトラアルキルアンモニウム基やイミダゾリウム基が特に好ましい。前記Ｒにイオン性官能基を有している場合は、その対イオンは特に限定されないが、カチオンとしてはアルカリ金属イオン、アルカリ土類金属イオン、テトラアルキルアンモニウムイオン、テトラアルキルホスホニウムイオン、イミダゾリウムイオンなどが挙げられ、アニオンとしてはアミドアニオン、過塩素酸イオン、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオン、トリフルオロメチルスルホン酸イオンなどが挙げられる。 As an ionic functional group in said R, a cationic tetraalkyl ammonium group, an imidazolium group, a tetraalkyl phosphonium group; anionic phosphate group, a carboxylate group, a nitrate group etc. are mentioned. From the viewpoint of cycle characteristics, cationic functional groups are preferable, and from the viewpoint of gas suppression, tetraalkyl ammonium groups and imidazolium groups are particularly preferable. When R has an ionic functional group, its counter ion is not particularly limited, but as a cation, an alkali metal ion, an alkaline earth metal ion, a tetraalkyl ammonium ion, a tetra alkyl phosphonium ion, an imidazolium ion Examples of the anion include amide anion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethylsulfonate ion and the like.
シルセスキオキサン構造を有する塩の量としては非水電解質１００重量％に対して０．０１％以上であれば良いが、サイクル特性の観点から０．０５％以上１０％以下が好ましく、最もバランスが良いことから０．１％以上５％以下が特に好ましい。 The amount of the salt having a silsesquioxane structure may be 0.01% or more based on 100% by weight of the non-aqueous electrolyte, but is preferably 0.05% or more and 10% or less from the viewpoint of cycle characteristics, and the most balanced 0.1% or more and 5% or less is particularly preferable because
非水電解質は、あらかじめ正極、負極およびセパレータに含ませてもよいし、正極と負極との間にセパレータを配置したものを積層した後に添加してもよい。また、非水溶媒に溶質を溶解させた電解液を高分子に含浸させたゲル電解質などを用いることができる。 The non-aqueous electrolyte may be contained in advance in the positive electrode, the negative electrode and the separator, or may be added after laminating one in which the separator is disposed between the positive electrode and the negative electrode. Alternatively, a gel electrolyte in which a polymer is impregnated with an electrolytic solution in which a solute is dissolved in a non-aqueous solvent can be used.
＜５．外装材＞
本発明に係る外装材の材料としては、熱融着により封止することが出来、外部からの水分の侵入を防ぎ、逆に内部から非水電解質が漏洩することを防ぐことが出来るラミネートフィルムを用いる。具体的な例としては、金属箔にヒートシール用の熱可塑性樹脂層を設けた複合フィルムが挙げられる。金属箔は外部からの水分の侵入を防ぎつつシート全体の強度を向上させるものであれば特に限定されないが、水分遮断性と重量ならびにコストの面からアルミ箔が好適に用いられ得る。シート全体の強度が確保できるのであれば、金属箔の代わりに蒸着やスパッタリングなどにより金属層を設けても良い。
<5. Exterior material>
As a material of the packaging material according to the present invention, a laminate film which can be sealed by heat fusion, can prevent the entry of moisture from the outside, and can prevent the non-aqueous electrolyte from leaking from the inside conversely Use. A specific example is a composite film in which a thermoplastic resin layer for heat sealing is provided on a metal foil. The metal foil is not particularly limited as long as it improves the strength of the entire sheet while preventing the entry of moisture from the outside, but aluminum foil may be suitably used from the viewpoint of water blocking property, weight and cost. If the strength of the entire sheet can be secured, a metal layer may be provided by vapor deposition or sputtering instead of metal foil.
熱可塑性樹脂層の組成については特に限定されないが、ヒートシール可能な温度範囲ならびに非水電解質の遮断性の観点から、ポリエチレンやポリプロピレンが好適に用いられ得る。 The composition of the thermoplastic resin layer is not particularly limited, but polyethylene and polypropylene can be suitably used from the viewpoint of the heat sealable temperature range and the blocking property of the non-aqueous electrolyte.
金属箔と熱可塑性樹脂との密着性を向上させるため、両者の間に接着層を設けていても良いし、金属箔の酸化防止のため、熱可塑性樹脂層を設けるのとは反対側の面に、保護層を設けていても良い。 An adhesive layer may be provided between the metal foil and the thermoplastic resin in order to improve the adhesion between the metal foil and the thermoplastic resin, and the surface opposite to the thermoplastic resin layer may be provided to prevent oxidation of the metal foil. In addition, a protective layer may be provided.
＜６．非水電解質二次電池＞
本発明の非水電解質二次電池の正極および負極は、集電体の両面に同じ電極を形成させた形態であってもよく、集電体の片面に正極、一方の面に負極を形成させた形態、すなわち、バイポーラ電極であってもよい。
<6. Nonaqueous electrolyte secondary battery>
The positive electrode and the negative electrode of the non-aqueous electrolyte secondary battery of the present invention may be in the form in which the same electrode is formed on both sides of the current collector. The positive electrode is formed on one side of the current collector, and the negative electrode is formed on one side. Alternatively, it may be a bipolar electrode.
本発明の非水電解質二次電池は、正極側と負極側との間にセパレータを配置したものを捲回したものであってもよいし、積層したものであってもよい。正極、負極、およびセパレータには、リチウムイオン伝導を担う非水電解質が含まれている。 The non-aqueous electrolyte secondary battery of the present invention may be one in which a separator is disposed between the positive electrode side and the negative electrode side may be wound or may be stacked. The positive electrode, the negative electrode, and the separator contain a non-aqueous electrolyte responsible for lithium ion conduction.
本発明の非水電解質二次電池における電極活物質層の面積は電池の設計によって適宜選択することができるが、サイクル安定性、安全性の観点から下記式（４）を満たすことが好ましい。 The area of the electrode active material layer in the non-aqueous electrolyte secondary battery of the present invention can be appropriately selected depending on the design of the battery, but it is preferable to satisfy the following formula (4) from the viewpoint of cycle stability and safety.
但し、Ａは正極活物質層の面積、Ｂは負極活物質層の面積を示す。 Here, A represents the area of the positive electrode active material layer, and B represents the area of the negative electrode active material layer.
また、負極活物質層とセパレータとの面積比は特に限定されないが、下記式（５）を満たすことが好ましい。 Further, the area ratio of the negative electrode active material layer to the separator is not particularly limited, but it is preferable to satisfy the following formula (5).
但し、Ｂは負極活物質層の面積、Ｃはセパレータの面積を示す。 However, B shows the area of a negative electrode active material layer, C shows the area of a separator.
本発明の非水電解質二次電池における正極の電気容量と負極の電気容量との比は、下記式（６）を満たすことが好ましい。 The ratio of the electric capacity of the positive electrode to the electric capacity of the negative electrode in the non-aqueous electrolyte secondary battery of the present invention preferably satisfies the following formula (6).
但し、上記式（６）中、Ｅは正極１ｃｍ２あたりの電気容量を示し、Ｄは負極１ｃｍ２あたりの電気容量を示す。 However, in the above formula (6), E denotes an electric capacity per positive electrode 1 cm 2, D represents an electric capacitance per negative electrode 1 cm 2.
本発明の非水電解質二次電池は、上記積層体を捲回、あるいは複数積層した後にラミネートフィルムで外装してもよいし、角形、楕円形、円筒形、コイン形、ボタン形、シート形の金属缶で外装してもよい。外装には発生したガスを放出するための機構が備わっていてもよい。積層体の積層数は、所望の電圧値、電池容量を発現するまで積層させることができる。 The non-aqueous electrolyte secondary battery of the present invention may be coated with a laminate film after winding or laminating a plurality of the above-mentioned laminates, and may be square, oval, cylindrical, coin, button or sheet You may coat with a metal can. The exterior may have a mechanism for releasing the generated gas. The number of stacked layers can be stacked until a desired voltage value and battery capacity are developed.
＜７．組電池＞
本発明の非水電解質二次電池は、複数接続することによって組電池とすることができる。本発明の組電池は、所望の大きさ、容量、電圧によって適宜直列、並列に接続することによって作製することができる。また、各電池の充電状態の確認、安全性向上のため、前記組電池に制御回路が付属されていることが好ましい。
<7. Battery assembly>
The non-aqueous electrolyte secondary battery of the present invention can be made into an assembled battery by connecting a plurality of batteries. The battery pack of the present invention can be produced by connecting in series and in parallel, as required, in accordance with the desired size, capacity and voltage. Further, it is preferable that a control circuit be attached to the assembled battery in order to confirm the state of charge of each battery and to improve the safety.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更可能である。 EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited at all by these examples, and can be appropriately modified without departing from the scope of the present invention.
（正極の製造例）
正極に用いる正極活物質として、スピネル型のマンガン酸リチウム（Ｌｉ１．１Ａｌ０．１Ｍｎ１．８Ｏ４）を用いた。
(Production example of positive electrode)
As a positive electrode active material used for the positive electrode, spinel-type lithium manganate (Li 1.1 Al 0.1 Mn 1.8 O 4 ) was used.
スピネル型のマンガン酸リチウム（Ｌｉ１．１Ａｌ０．１Ｍｎ１．８Ｏ４）、導電助材（アセチレンブラック）、およびバインダー（ＰＶｄＦ）を、それぞれ固形分濃度で１００重量部、５重量部、および５重量部となるように混合し、スラリーを作製した。なお、バインダーは固形分濃度５ｗｔ％のＮ−メチル−２−ピロリドン（ＮＭＰ）溶液に調整したものを使用し、後述の塗工をしやすいように、さらにＮＭＰを加えて粘度調整した。 100 parts by weight and 5 parts by weight in solid concentration of spinel type lithium manganate (Li 1.1 Al 0.1 Mn 1.8 O 4 ), conductive auxiliary (acetylene black) and binder (PVdF) And 5 parts by weight were mixed to prepare a slurry. The binder was adjusted to a solid content concentration of 5 wt% in N-methyl-2-pyrrolidone (NMP) solution, and the viscosity was adjusted by further adding NMP so as to facilitate coating described later.
このスラリーをアルミニウム箔（２０μｍ）に片面塗工して１２０℃のオーブンで乾燥させた後、裏面も同様に塗工・乾燥を行い、さらに１７０℃で真空乾燥することによって正極（片面５０ｃｍ２）を作製した。 This slurry is coated on one side on an aluminum foil (20 μm) and dried in an oven at 120 ° C., and the back is also coated and dried in the same manner, and further vacuum dried at 170 ° C. to obtain a positive electrode (50 cm 2 on one side). Was produced.
正極の容量は次の充放電試験で測定した。 The capacity of the positive electrode was measured by the following charge and discharge test.
前述と同様にアルミニウム箔の片面に塗工した電極を１６ｍｍΦに打ち抜き動作極、Ｌｉ金属を１６ｍｍΦに打ち抜き対極とした。これらの電極を用いて、動作極（片面塗工）／セパレータ／Ｌｉ金属の順に試験セル（ＨＳセル、宝泉社製）内に積層し、非水電解質（エチレンカーボネート／ジメチルカーボネート＝３／７ｖｏｌ％、ＬｉＰＦ６ １ｍｏｌ／Ｌ）を０．１５ｍＬ入れ、半電池を作製した。この半電池を２５℃で一日放置した後、充放電試験装置（ＨＪ１００５ＳＤ８、北斗電工社製）に接続した。この半電池を２５℃、０．４ｍＡで定電流充電（終止電圧：４．５Ｖ）および定電流放電（終止電圧：３．５Ｖ）を５回繰り返し、５回目の結果を放電容量の正極の容量とした。その結果、正極の容量は、１．０ｍＡｈ／ｃｍ２であった。 The electrode coated on one side of the aluminum foil in the same manner as described above was punched to 16 mm in diameter, and the Li metal was punched to 16 mm in diameter. Using these electrodes, the working electrode (single-sided coating) / separator / Li metal is laminated in the order of the test cell (HS cell, manufactured by Hohsen Co., Ltd.), and the non-aqueous electrolyte (ethylene carbonate / dimethyl carbonate = 3/7 vol %, LiPF 6 1 mol / L) was added to make a half cell. The half battery was left at 25 ° C. for a day, and then connected to a charge / discharge test apparatus (HJ1005SD8, manufactured by Hokuto Denko Corporation). This half-cell is repeated five times at 25 ° C., 0.4 mA constant current charge (final voltage: 4.5 V) and constant current discharge (final voltage: 3.5 V), and the fifth result is the capacity of the positive electrode of the discharge capacity And As a result, the capacity of the positive electrode was 1.0 mAh / cm 2 .
（負極の製造例）
負極活物質として、平均粒子径が５μｍ、比表面積が４ｍ２／ｇのスピネル型のチタン酸リチウム（Ｌｉ４／３Ｔｉ５／３Ｏ４）を用いた。この負極活物質、導電助材（アセチレンブラック）、およびバインダー（ＰＶｄＦ）を、それぞれ固形分濃度で１００重量部、５重量部、および５重量部となるように混合し、スラリーを作製した。なお、バインダーは固形分濃度５ｗｔ％のＮＭＰ溶液に調製したものを使用し、後述の塗工をしやすいように、さらにＮＭＰを加えて粘度調整した。このスラリーをアルミニウム箔（２０μｍ）に塗工した後に、１２０℃のオーブンで乾燥させた後、さらに１７０℃で真空乾燥することによって負極（５５ｃｍ２）を作製した。
(Example of production of negative electrode)
A spinel type lithium titanate (Li 4/3 Ti 5/3 O 4 ) having an average particle diameter of 5 μm and a specific surface area of 4 m 2 / g was used as the negative electrode active material. The negative electrode active material, the conductive additive (acetylene black), and the binder (PVdF) were mixed so as to have a solid content concentration of 100 parts by weight, 5 parts by weight, and 5 parts by weight, respectively, to prepare a slurry. The binder used was prepared in an NMP solution with a solid content concentration of 5 wt%, and the viscosity was adjusted by further adding NMP so as to facilitate coating described later. The slurry was applied to an aluminum foil (20 μm), dried in an oven at 120 ° C., and then vacuum dried at 170 ° C. to produce a negative electrode (55 cm 2 ).
負極の容量は次の充放電試験で測定した。 The capacity of the negative electrode was measured by the following charge and discharge test.
前述と同様の条件でアルミニウム箔の片面に電極を塗工し、１６ｍｍΦに打ち抜き動作極を作製した。Ｌｉ金属を１６ｍｍΦに打ち抜き対極とした。これらの電極を用いて、動作極（片面塗工）／セパレータ／Ｌｉ金属の順に試験セル（ＨＳセル、宝泉社製）内に積層し、非水電解質（エチレンカーボネート／ジメチルカーボネート＝３／７ｖｏｌ％、ＬｉＰＦ６ １ｍｏｌ／Ｌ）を０．１５ｍＬ入れ、半電池を作製した。この半電池を２５℃で一日放置した後、充放電試験装置（ＨＪ１００５ＳＤ８、北斗電工社製）に接続した。この半電池を２５℃、０．４ｍＡで定電流放電（終止電圧：１．０Ｖ）および定電流充電（終止電圧：２．０Ｖ）を５回繰り返し、５回目の放電容量の結果を負極の容量とした。その結果、負極の容量は、１．２ｍＡｈ／ｃｍ２であった。 An electrode was coated on one side of the aluminum foil under the same conditions as described above, and a punching operation pole was produced to 16 mm diameter. The Li metal was punched out to 16 mm in diameter and used as a counter electrode. Using these electrodes, the working electrode (single-sided coating) / separator / Li metal is laminated in the order of the test cell (HS cell, manufactured by Hohsen Co., Ltd.), and the non-aqueous electrolyte (ethylene carbonate / dimethyl carbonate = 3/7 vol %, LiPF 6 1 mol / L) was added to make a half cell. The half battery was left at 25 ° C. for a day, and then connected to a charge / discharge test apparatus (HJ1005SD8, manufactured by Hokuto Denko Corporation). This half-cell is subjected to constant current discharge (final voltage: 1.0 V) and constant current charge (final voltage: 2.0 V) at 25 ° C. and 0.4 mA five times, and the result of the fifth discharge capacity is the negative electrode capacity And As a result, the capacity of the negative electrode was 1.2 mAh / cm 2 .
（実施例１〜８、比較例１〜３）
製造例で作製した正極、負極を用い、セパレータは、セルロース系不職布（２５μｍ、６０ｃｍ２）を用いた。最初に、正極、負極、およびセパレータを、セパレータ／負極／セパレータ／正極／セパレータ／負極／セパレータの順に積層し、次に、正極および負極それぞれの未塗工部にアルミニウムタブを振動溶着させた後に、上下から二枚のアルミラミネートフィルムで挟み、３辺を１８０℃×７秒で二回ヒートシールして融着させた。ここに各種シルセスキオキサン構造を有する塩を含有する非水電解質（エチレンカーボネート／プロピレンカーボネート／エチルメチルカーボネート＝１５／１５／７０ｖｏｌ％、ＬｉＰＦ６ １ｍｏｌ／Ｌ）６ｍＬを入れた後に、減圧しながら残りの辺を１８０℃×７秒で二回ヒートシールし、非水電解質二次電池を得た。なお、実施例１〜６のシルセスキオキサン構造を有する塩の対イオンはテトラブチルアンモニウムイオン、実施例７、８のシルセスキオキサン構造を有する塩の対イオンはヘキサフルオロリン酸イオンである。
(Examples 1-8, comparative examples 1-3)
Using the positive electrode and the negative electrode produced in the production example, a cellulose non-woven cloth (25 μm, 60 cm 2 ) was used as a separator. First, the positive electrode, the negative electrode, and the separator are laminated in the order of separator / negative electrode / separator / positive electrode / separator / negative electrode / separator, and then, after vibration welding of aluminum tabs to uncoated portions of the positive electrode and negative electrode, respectively. The two sides of the laminate were sandwiched by two aluminum laminate films from above and below, and the three sides were heat sealed and fused twice at 180 ° C. for 7 seconds. After adding 6 mL of a non-aqueous electrolyte (ethylene carbonate / propylene carbonate / ethyl methyl carbonate = 15/15/70 vol%, LiPF 6 1 mol / L) containing a salt having various silsesquioxane structures here, the pressure is reduced while reducing pressure The remaining side was heat sealed twice at 180 ° C. for 7 seconds to obtain a non-aqueous electrolyte secondary battery. The counter ion of the salt having a silsesquioxane structure of Examples 1 to 6 is tetrabutyl ammonium ion, and the counter ion of the salt having a silsesquioxane structure of Examples 7 and 8 is hexafluorophosphate ion. .
（非水電解質二次電池のサイクル特性評価）
実施例または比較例で作製した非水電解質二次電池を、充放電装置（ＨＪ１００５ＳＤ８、北斗電工社製）に接続し、エージング工程を経た後に充放電サイクル運転を行った。
(Evaluation of cycle characteristics of non-aqueous electrolyte secondary battery)
The non-aqueous electrolyte secondary battery produced in the example or the comparative example was connected to a charge / discharge device (HJ1005SD8, manufactured by Hokuto Denko Co., Ltd.), and after the aging step, charge / discharge cycle operation was performed.
エージング工程では、各非水電解質二次電池を満充電（２．７Ｖ）にしたのちに、６０℃で１６８時間放置し、その後、室温(２５℃)まで徐冷した。 In the aging step, each non-aqueous electrolyte secondary battery was fully charged (2.7 V), allowed to stand at 60 ° C. for 168 hours, and then gradually cooled to room temperature (25 ° C.).
エージング工程後に、６０℃、２５ｍＡ定電流充電、５０ｍＡ定電流放電を５００回繰り返した。このときの充電終止電圧および放電終止電圧はそれぞれ２．７Ｖおよび２．０Ｖとした。サイクル特性の安定性は、１回目の放電容量を１００としたときの、５００回目の放電容量の維持率で評価した。ガス発生が無く、５００回目の放電容量維持率で８０％以上を良好、８０％未満を不良とした。この結果を表１に記載した。なお、ガス発生の判定は、充放電サイクル運転前後の電池の体積をアルキメデス法で測定し、その増加分であるガス発生量が０．５ｍＬ／Ａｈ未満であった場合をガス発生なし、０．５ｍＬ／Ａｈ以上であった場合をガス発生有とした。 After the aging step, 60 ° C., 25 mA constant current charge and 50 mA constant current discharge were repeated 500 times. The charge termination voltage and the discharge termination voltage at this time were 2.7 V and 2.0 V, respectively. The stability of the cycle characteristics was evaluated by the maintenance rate of the 500th discharge capacity when the first discharge capacity was 100. There was no gas generation, and 80% or more of the 500th discharge capacity maintenance rate was regarded as good, and less than 80% as failure. The results are shown in Table 1. In addition, determination of gas generation measures the volume of the battery before and behind charge / discharge cycle driving | operation by the Archimedes method, and the gas generation amount which is the increase is less than 0.5 mL / Ah that there is no gas generation, 0. It was regarded as having gas generation when it was 5 mL / Ah or more.
実施例１〜８はシルセスキオキサン構造を有する塩を含有していることにより、負極近傍に良好な膜が形成され、ガス発生が抑制された上、良好なサイクル特性を有している。 By containing the salt having a silsesquioxane structure, Examples 1 to 8 form a good film in the vicinity of the negative electrode, suppress gas generation, and have good cycle characteristics.
これに対して、比較例１は、シルセスキオキサン構造を有する塩を添加していないため、保護膜が形成されず、負極の異常活性点により電解液が分解され、ガスが発生しているものと考えられる。比較例２、３は、シルセスキオキサンが塩となっておらず、非水電解質への溶解度が低いため良好な膜形成ができないためにガス発生が抑制できなかったものと推察される。 On the other hand, in Comparative Example 1, since the salt having the silsesquioxane structure is not added, the protective film is not formed, and the electrolytic solution is decomposed by the abnormal active point of the negative electrode to generate gas. It is considered to be a thing. In Comparative Examples 2 and 3, since silsesquioxane is not in the form of a salt and the solubility in the non-aqueous electrolyte is low, it is presumed that gas generation can not be suppressed because a good film can not be formed.
以上の結果から、非水電解質二次電池において、負極活物質としてチタン含有酸化物を含み、非水電解質に、シルセスキオキサン構造を有する塩を含有してなり、前記シルセスキオキサン構造を有する塩を、非水電解質１００重量％に対して０．０１重量％以上含有させることで、ガス発生が抑制され、優れたサイクル特性を有することが明らかとなった。
From the above results, in the non-aqueous electrolyte secondary battery, the non-aqueous electrolyte contains a titanium-containing oxide as a negative electrode active material, and the non-aqueous electrolyte contains a salt having a silsesquioxane structure, and By containing 0.01% by weight or more based on 100% by weight of the non-aqueous electrolyte, it was revealed that the generation of gas was suppressed and the excellent cycle characteristics were obtained.
Claims (8)
前記負極が、負極活物質としてチタン含有酸化物を含み、
前記非水電解質が、シルセスキオキサン構造を有する塩を含有してなり、
前記シルセスキオキサン構造を有する塩は、
分子内にフッ化物イオン及び／若しくは塩化物イオンを包接し、
並びに／又は、
カチオン性及び／若しくはアニオン性のイオン性官能基を有し、
前記シルセスキオキサン構造を有する塩が、前記非水電解質１００重量％に対して０．０１重量％以上であることを特徴とする、非水電解質二次電池。 What is claimed is: 1. A secondary battery comprising: a negative electrode; a positive electrode; and a non-aqueous electrolyte interposed between the negative electrode and the positive electrode,
The negative electrode contains a titanium-containing oxide as a negative electrode active material,
The non-aqueous electrolyte comprises a salt having a silsesquioxane structure,
The salt having the silsesquioxane structure is
Include fluoride ion and / or chloride ion in the molecule,
And / or
It has a cationic and / or anionic ionic functional group,
The non-aqueous electrolyte secondary battery, wherein the salt having a silsesquioxane structure is 0.01% by weight or more based on 100% by weight of the non-aqueous electrolyte.
An assembled battery comprising a plurality of non-aqueous electrolyte secondary batteries according to any one of claims 1 to 7 connected to one another.
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