CN109964357A - 非水电解质二次电池 - Google Patents
非水电解质二次电池 Download PDFInfo
- Publication number
- CN109964357A CN109964357A CN201780065114.6A CN201780065114A CN109964357A CN 109964357 A CN109964357 A CN 109964357A CN 201780065114 A CN201780065114 A CN 201780065114A CN 109964357 A CN109964357 A CN 109964357A
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- CN
- China
- Prior art keywords
- secondary battery
- mass
- anhydride
- electrolyte
- aqueous electrolyte
- Prior art date
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- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 55
- -1 cyclic carboxylic acids acid anhydride Chemical class 0.000 claims abstract description 54
- 239000011737 fluorine Substances 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 26
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 9
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 5
- YXFXSZUWEMYJSJ-UHFFFAOYSA-N 3,5-bis(ethenyl)-1,4-dioxane-2,6-dione Chemical compound C(=C)C1OC(C(=O)OC1=O)C=C YXFXSZUWEMYJSJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 2
- KZCSJWFLPQFDNW-UHFFFAOYSA-N 1-ethenylpyrrole-2,5-dione Chemical compound C=CN1C(=O)C=CC1=O KZCSJWFLPQFDNW-UHFFFAOYSA-N 0.000 claims description 2
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 claims description 2
- SVIAAUKJQZPUCA-UHFFFAOYSA-N 3,5-dimethyl-1,4-dioxane-2,6-dione Chemical compound CC1OC(C)C(=O)OC1=O SVIAAUKJQZPUCA-UHFFFAOYSA-N 0.000 claims description 2
- QJXHNHMORUZUGS-UHFFFAOYSA-N 3-ethyl-1,4-dioxane-2,6-dione Chemical compound C(C)C1C(=O)OC(CO1)=O QJXHNHMORUZUGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- HQRXOJFPSKBRSE-UHFFFAOYSA-N 3-ethenyl-1,4-dioxane-2,6-dione Chemical compound C(=C)C1C(=O)OC(CO1)=O HQRXOJFPSKBRSE-UHFFFAOYSA-N 0.000 claims 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 abstract description 14
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003923 2,5-pyrrolediones Chemical class 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000009194 climbing Effects 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- YKSSSKBJDZDZTD-XVNBXDOJSA-N (E)-isoeugenyl benzyl ether Chemical compound COC1=CC(\C=C\C)=CC=C1OCC1=CC=CC=C1 YKSSSKBJDZDZTD-XVNBXDOJSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- CMTIUBRAGNDCRZ-UHFFFAOYSA-N 1-(2-hydroxyethoxy)but-3-en-2-ol Chemical compound C(=C)C(COCCO)O CMTIUBRAGNDCRZ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical class CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SGGPSSHEWWGIPZ-UHFFFAOYSA-N 4,5-bis(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1OC(=O)OC1C(F)(F)F SGGPSSHEWWGIPZ-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- BTXFOZITJDJTGJ-UHFFFAOYSA-N 4-(fluoromethyl)-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1CF BTXFOZITJDJTGJ-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical class CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- WKFDWSVVMAKCDI-UHFFFAOYSA-N C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] Chemical compound C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] WKFDWSVVMAKCDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910020596 CmF2m+1SO2 Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013164 LiN(FSO2)2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005587 carbonate group Chemical group 0.000 description 1
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- FUGIIBWTNARRSF-UHFFFAOYSA-N decane-5,6-diol Chemical compound CCCCC(O)C(O)CCCC FUGIIBWTNARRSF-UHFFFAOYSA-N 0.000 description 1
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- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种非水电解质二次电池,其具备正极、负极和非水电解质,前述非水电解质含有:包含含氟环状碳酸酯的非水溶剂、N‑乙基马来酰亚胺等马来酰亚胺化合物和二甘醇酐等环状羧酸酐。
Description
技术领域
本发明涉及非水电解质二次电池的技术。
背景技术
例如,专利文献1公开了一种非水电解质二次电池,其具备正极、负极和包含含氟环状碳酸酯的电解液。专利文献1中记载了通过使用包含含氟环状碳酸酯的电解液而使在室温下的循环特性得以改善。
现有技术文献
专利文献
专利文献1:日本特开2013-182807号公报
发明内容
然而,使用了包含含氟环状碳酸酯的电解液的非水电解质二次电池的情况,在室温下的循环特性得以改善,另一方面存在高温环境下(例如,40℃以上)的电池的电阻(以下称为电阻)上升这样的问题。在高温环境下的电阻的上升有导致在高温环境下保存电池后的容量恢复率降低、在高温环境下的充放电循环时的容量降低的担心。
因此,本发明的目的在于提供能够抑制在高温环境下的电阻上升的非水电解质二次电池。
本发明的一个方式的非水电解质二次电池具备正极、负极和非水电解质,
所述非水电解质含有:包含含氟环状碳酸酯的非水溶剂、马来酰亚胺化合物和下式所示的环状羧酸酐。
(式中,R1~R4独立地为H、烷基、链烯基或芳基。)
根据本发明的一个方式的非水电解质二次电池,能够抑制在高温环境下的电阻上升。
具体实施方式
如上所述,使用了包含含氟环状碳酸酯的电解液的非水电解质二次电池的情况,存在在高温环境下的电阻上升这样的问题。因此,本发明人等进行了深入研究,结果发现:通过在包含含氟环状碳酸酯的非水电解质中添加以下详述的马来酰亚胺化合物和环状羧酸酐,从而能够抑制在高温环境下的电阻上升。作为其机理,可推测以下情况。
具备包含含氟环状碳酸酯的非水电解质的非水电解质二次电池的情况,在初始充电时,一部分含氟环状碳酸酯在负极表面被分解,在负极表面形成覆膜(固体电解质中间相(Solid Electrolyte Interphase)覆膜、以下称为SEI覆膜)。通常,通过形成含氟环状碳酸酯来源的SEI覆膜,而可抑制在之后的充放电过程中发生的非水电解质的分解,但含氟环状碳酸酯来源的SEI覆膜缺乏热稳定性,因此在高温环境下,该SEI覆膜被破坏。其结果,在充放电过程发生的非水电解质成分的分解进行,电绝缘性的副反应产物堆积于负极上,由此使电池的电阻上升。然而,通过使含氟环状碳酸酯和以下详述的马来酰亚胺化合物共存于非水电解质中,而使马来酰亚胺化合物的马来酰亚胺基与非水电解质中的碳酸酯基等发生反应,并在负极表面形成马来酰亚胺基来源的覆膜。可认为:该覆膜具有源自马来酰亚胺基的高的热稳定性,对含氟环状碳酸酯来源的SEI覆膜赋予耐热性。其结果,在高温环境下的SEI覆膜的破坏得到抑制,因此可抑制非水电解质的进一步的分解。但是,含氟环状碳酸酯和马来酰亚胺化合物共存的非水电解质的情况,形成于负极表面上的SEI覆膜原本是离子传导性低的膜,因此仅通过使含氟环状碳酸酯和马来酰亚胺化合物共存的情况下,高温环境下的电池的电阻上升抑制效果并不充分。然而,通过在非水电解质中共存以下详述的环状羧酸酐,从而能够在负极表面形成离子传导性高的SEI覆膜。由此,可认为通过本发明的非水电解质二次电池,在负极表面形成具有高的耐热性且具有高的离子传导性的SEI覆膜,因此能够抑制在高温环境下的电阻上升。
以下对实施方式的非水电解质二次电池的一例进行说明。
作为实施方式的一例的非水电解质二次电池具备正极、负极和非水电解质。在正极与负极之间设置分隔件是适宜的。具体而言,具有将隔着分隔件卷绕正极和负极而成的卷绕型的电极体、及非水电解质收纳于外壳体中的结构。或者,还可以代替卷绕型的电极体,适用隔着分隔件层叠正极和负极而成的层叠型的电极体等其它形态的电极体。另外,作为非水电解质二次电池的形态,没有特别限定,可以示例出圆筒型、方型、硬币型、纽扣型、层压型等。
[非水电解质]
非水电解质含有:包含含氟环状碳酸酯的非水溶剂、马来酰亚胺化合物、环状羧酸酐和电解质盐。非水电解质不限定于液体电解质(非水电解液),可以是使用了凝胶状聚合物等的固体电解质。
非水溶剂中包含的含氟环状碳酸酯只要是含有至少1个氟的环状碳酸酯就没有特别限制,例如可列举出:单氟代碳酸亚乙酯(FEC)、1,2-二氟代碳酸亚乙酯、1,2,3-三氟代碳酸亚丙酯、2,3-二氟-2,3-碳酸亚丁酯、1,1,1,4,4,4-六氟-2,3-碳酸亚丁酯等。这些当中,从抑制高温时的氢氟酸的产生量的方面等考虑,优选FEC。
例如相对于非水溶剂的总体积,含氟环状碳酸酯的含量优选为0.1体积%以上且30体积%以下、更优选为10体积%以上且20体积%以下。含氟环状碳酸酯的含量低于0.1体积%时,含氟环状碳酸酯来源的SEI覆膜的生成量少,有时使室温下的循环特性降低。另外,含氟环状碳酸酯的含量超过30体积%时,含氟环状碳酸酯来源的SEI覆膜的生成量增多,有时无法充分地发挥马来酰亚胺化合物和环状羧酸酐的添加效果(在高温环境下的电阻上升抑制效果)。
非水溶剂除了含氟环状碳酸酯以外还可以包含例如非氟系溶剂。作为非氟系溶剂,可以示例出:环状碳酸酯类、链状碳酸酯类、羧酸酯类、环状醚类、链状醚类、乙腈等腈类、二甲基甲酰胺等酰胺类、和它们的混合溶剂。
作为上述环状碳酸酯类的例子,可列举出:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯等。作为上述链状碳酸酯类的例子,可列举出:碳酸二甲酯、碳酸甲乙酯(EMC)、碳酸二乙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲基异丙酯等。
作为上述羧酸酯类的例子,可列举出:乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯(MP)、丙酸乙酯、γ-丁内酯等。
作为上述环状醚类的例子,可列举出:1,3-二氧戊环、4-甲基-1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、1,2-环氧丁烷、1,3-二氧杂环己烷、1,4-二氧杂环己烷、1,3,5-三氧杂环己烷、呋喃、2-甲基呋喃、1,8-桉树脑、冠醚等。
作为上述链状醚类的例子,可列举出:1,2-二甲氧基乙烷、二乙醚、二丙醚、二异丙醚、二丁醚、二己醚、乙基乙烯基醚、丁基乙烯基醚、甲基苯基醚、乙基苯基醚、丁基苯基醚、戊基苯基醚、甲氧基甲苯、苄基乙基醚、二苯基醚、二苄基醚、邻二甲氧基苯、1,2-二乙氧基乙烷、1,2-二丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、1,1-二甲氧基甲烷、1,1-二乙氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚等。
非水电解质中包含的马来酰亚胺化合物只要是在分子结构中具有至少1个马来酰亚胺基的化合物就没有特别限定,例如可列举出:单马来酰亚胺化合物、双马来酰亚胺化合物等,从试剂成本、作业性、溶解性等的观点出发,优选单马来酰亚胺化合物。
单马来酰亚胺化合物例如由下式表示。
(式中,R5为氢基、具有芳香族环或脂肪族烃的一价的有机基团。)。作为具有芳香族环或脂肪族烃的一价的有机基团,例如可列举出:烷基、环烷基、单环式或多环式的芳基等。
作为非水电解质中包含的单马来酰亚胺化合物,具体而言,可列举出:N-甲基马来酰亚胺(下述结构式(A))、N-乙基马来酰亚胺(下述结构式(B))、N-丙基马来酰亚胺(下述结构式(C))、N-丁基马来酰亚胺(下述结构式(D))、N-乙烯基马来酰亚胺(下述结构式(E))、N-苯基马来酰亚胺(下述结构式(F))等。其中,从在高温环境下的电阻的上升抑制效果等的观点出发,优选N-乙基马来酰亚胺、N-苯基马来酰亚胺。
从在高温环境下的电阻的上升抑制效果等的观点出发,非水电解质中包含的马来酰亚胺化合物的含量例如相对于非水电解质的总质量,优选0.1质量%以上且1.5质量%以下的范围、更优选0.1质量%以上且0.5质量%以下的范围。
非水电解质中包含的环状羧酸酐由下式表示。
(式中,R1~R4独立地为氢、烷基、链烯基或芳基。)
作为非水电解质中包含的环状羧酸酐,具体而言,可列举出:二甘醇酐、甲基二甘醇酐、二甲基二甘醇酐、乙基二甘醇酐、甲氧基二甘醇酐、乙氧基二甘醇酐、乙烯基二甘醇酐、烯丙基二甘醇酐、二乙烯基二甘醇酐、二乙烯基二甘醇酐等。其中,从在高温环境下的电阻的上升抑制效果等的观点出发,优选二甘醇酐。
从在高温环境下的电阻的上升抑制效果等的观点出发,非水电解质中包含的环状羧酸酐的含量例如相对于非水电解质的总质量,优选0.1质量%以上且2.5质量%以下的范围、更优选0.1质量%以上且1.0质量%以下的范围、进一步优选0.1质量%以上且0.5质量%以下的范围。
非水电解质中包含的电解质盐优选为锂盐。锂盐可以使用现有的非水电解质二次电池中作为支持盐通常使用的物质。作为具体例,可列举出:LiPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiN(FSO2)2、LiN(ClF2l+1SO2)(CmF2m+1SO2)(l,m为0以上的整数)、LiC(CpF2p+1SO2)(CqF2q+1SO2)(CrF2r+1SO2)(p、q、r为1以上的整数)、Li[B(C2O4)2](双乙二酸硼酸锂(LiBOB))、Li[B(C2O4)F2]、Li[P(C2O4)F4]、Li[P(C2O4)2F2]等。这些锂盐可以使用1种,另外还可以组合使用2种以上。
[正极]
正极由例如金属箔等正极集电体和形成于正极集电体上的正极活性物质层构成。正极集电体可以使用铝等在正极的电位范围内稳定的金属的箔、将该金属配置于表层的薄膜等。正极例如可以通过如下方式制作:将包含正极活性物质、粘结材料等的正极复合材料浆料涂布于正极集电体上,使涂膜干燥后进行压延,而在正极集电体上形成正极活性物质层。
作为正极活性物质,可列举出锂过渡金属复合氧化物等,具体而言可列举出:钴酸锂、锰酸锂、镍酸锂、锂镍锰复合氧化物、锂镍钴复合氧化物等。另外,还可以在这些锂过渡金属复合氧化物中添加Al、Ti、Zr、Nb、B、W、Mg、Mo等。
作为导电剂,可以单独使用炭黑、乙炔黑、科琴黑、石墨等碳粉末或组合使用2种以上。
作为粘结剂,可列举出氟系高分子、橡胶系高分子等。例如,作为氟系高分子,可列举出:聚四氟乙烯(PTFE)、聚偏氟乙烯(PVdF)或它们的改性物等,作为橡胶系高分子,可列举出:乙烯-丙烯-异戊二烯共聚物、乙烯-丙烯-丁二烯共聚物等,它们可以单独使用或组合使用2种以上。
[负极]
负极具备例如金属箔等负极集电体和形成于负极集电体上的负极活性物质层。负极集电体可以使用铜等在负极的电位范围内稳定的金属的箔、将该金属配置于表层的薄膜等。负极活性物质层除了负极活性物质之外包含增稠剂、粘结剂是适宜的。负极例如可以通过如下方式制作:将负极活性物质、增稠剂和粘结剂设为规定的重量比,将分散于水中的负极合剂浆料涂布于负极集电体上,使涂膜干燥后进行压延而在负极集电体上形成负极活性物质层。
作为负极活性物质,可列举出能够吸藏/释放锂离子的碳材料、非碳材料等。作为碳材料,例如可列举出:石墨、难石墨性碳、易石墨性碳、纤维状碳、焦炭和炭黑等。作为非碳系材料,可列举出硅、锡和以它们为主的合金、氧化物等。
作为粘结剂,还可以与正极的情况同样地使用PTFE等,可以使用苯乙烯-丁二烯共聚物(SBR)或其改性物等。作为增稠剂,可以使用羧甲基纤维素(CMC)等。
[分隔件]
分隔件例如可使用具有离子透过性和绝缘性的多孔片等。作为多孔片的具体例,可列举出微多孔薄膜、织布、无纺布等。作为分隔件的材质,聚乙烯、聚丙烯等烯烃系树脂、纤维素等是适宜的。分隔件可以是具有纤维素纤维层和烯烃系树脂等热塑性树脂纤维层的层叠体。另外,可以是包含聚乙烯层和聚丙烯层的多层分隔件,还可以使用在分隔件的表面涂布了芳纶系树脂、陶瓷等材料的分隔件。
实施例
以下通过实施例对本发明进行进一步说明,但本发明不限定于以下的实施例。
<实施例1>
[正极的制作]
作为正极活性物质,使用通式LiNi0.8Co0.15Al0.05O2所示的锂复合氧化物。以该正极活性物质为100质量%、作为导电材料的乙炔黑为1质量%、作为粘结剂的聚偏氟乙烯为0.9质量%的方式进行混合,加入N-甲基-2-吡咯烷酮(NMP)制备了正极复合材料浆料。接着,利用刮刀法将正极复合材料浆料涂布于厚度15μm的铝制的正极集电体的两面,对涂膜进行压延,在正极集电体的两面形成了厚度70μm的正极活性物质层。将其作为正极。
[负极的制作]
以作为负极活性物质的石墨为100质量%、作为粘结材料的苯乙烯-丁二烯共聚物(SBR)为1质量%的方式进行混合,加入水制备了负极复合材料浆料。接着,利用刮刀法将负极复合材料浆料涂布于厚度10μm的铜制的负极集电体的两面,对涂膜进行压延,在负极集电体的两面形成了厚度100μm的负极活性物质层。将其作为负极。
[电解液的制备]
在以15:45:40的体积比混合了氟代碳酸亚乙酯(FEC)、碳酸甲乙酯(EMC)和碳酸二甲酯(DMC)的混合溶剂中,以成为1.3摩尔/L的浓度的方式溶解LiPF6,进而,使N-乙基马来酰亚胺(NEM)0.5质量%、二甘醇酐(DGA)0.5质量%溶解而制备了电解液。
[圆筒型电池的制作]
分别将上述的正极和负极裁切成规定的尺寸并安装电极片,隔着分隔件进行卷绕而制作了卷绕型的电极体。接着,在电极体的上方和下方配置了绝缘板的状态下将电极体收纳于直径18mm、高度65mm的实施了镀Ni的钢制的外装罐中,将负极片与电池外装罐的内侧底部熔接并将正极片与封口体的底板部熔接。此外,从外装罐的开口部注入上述的电解液,用封口体密闭外装罐而制作了圆筒型电池。
<实施例2>
制备电解液时,使N-乙基马来酰亚胺(NEM)0.5质量%、二甘醇酐(DGA)1.0质量%溶解而制备了电解液,除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<实施例3>
制备电解液时,使N-乙基马来酰亚胺(NEM)0.5质量%、二甘醇酐(DGA)1.5质量%溶解而制备了电解液,除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<实施例4>
制备电解液时,使N-乙基马来酰亚胺(NEM)1.0质量%、二甘醇酐(DGA)0.5质量%溶解而制备了电解液,除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<实施例5>
制备电解液时,使N-乙基马来酰亚胺(NEM)1.5质量%、二甘醇酐(DGA)0.5质量%溶解而制备了电解液,除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<实施例6>
制备电解液时,代替N-乙基马来酰亚胺(NEM),使用了N-苯基马来酰亚胺(NPM),除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<比较例1>
制备电解液时,未添加N-乙基马来酰亚胺(NEM)和二甘醇酐(DGA),除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<比较例2>
制备电解液时,未添加二甘醇酐(DGA),除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<比较例3>
制备电解液时,代替N-乙基马来酰亚胺(NEM),使用N-苯基马来酰亚胺(NPM),未添加二甘醇酐(DGA),除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
<比较例4>
制备电解液时,未添加N-乙基马来酰亚胺(NEM),除此以外与实施例1同样地制备了电解液。使用该电解液,与实施例1同样地制作了圆筒型电池。
[高温保存试验]
(电阻)
将实施例和比较例的各电池以0.3C的恒定电流进行充电直至电池电压为4.1V,以0.5C的恒定电流进行10秒放电。基于该放电前后的电压变化和放电电流值求出电阻。对于该电阻评价,在40℃的高温环境下放置前(第1天)和放置9个月后进行,求出以下的式子所示的电阻上升率。将该结果示于表1。
电阻上升率=(第9个月的电阻值/第1天的电阻值)×100
[高温循环试验]
(电阻)
在45℃的高温环境下,将实施例和比较例的各电池以0.5C的恒定电流进行充电直至电池电压为4.1V,以0.5C的恒定电流进行30秒放电。基于该放电前后的电压变化和放电电流值求出电阻。对于该电阻评价,在上述循环试验的第1次循环和第300次循环时进行,求出以下的式子所示的电阻上升率。将该结果示于表1。
电阻上升率=(第300次循环的电阻值/第1次循环的电阻值)×100
[表1]
NEM:N-乙基马来酰亚胺
NPM:N-苯基马来酰亚胺
DGA:二甘醇酐
实施例1~6的电池与电解液中不包含上述马来酰亚胺化合物和上述环状羧酸酐的比较例1的电池、包含上述马来酰亚胺化合物但不包含上述环状羧酸酐的比较例2、3的电池、及包含上述环状羧酸酐但不包含上述马来酰亚胺化合物的比较例4的电池相比,高温保存试验时的电阻上升率小。另外,在高温循环试验中也有实施例电池比比较例电池的电阻上升率小的倾向。由这些结果可以说:通过在电解液中添加上述环状羧酸酐和上述马来酰亚胺化合物这两者,从而能够抑制在高温环境下的电阻的上升。
另外,基于实施例1、2和3的电阻上升率的比较或实施例1、4和5的电阻上升率的比较,有随着马来酰亚胺化合物和环状羧酸酐的添加量的增加而电阻上升率增大的倾向,马来酰亚胺化合物和环状羧酸酐的添加量相对于非水电解质的总质量分别更优选0.5质量%以下。
Claims (6)
1.一种非水电解质二次电池,其为具备正极、负极和非水电解质的非水电解质二次电池,
所述非水电解质含有:包含含氟环状碳酸酯的非水溶剂、马来酰亚胺化合物和下式所示的环状羧酸酐,
式中,R1~R4独立地为H、烷基、链烯基或芳基。
2.根据权利要求1所述的非水电解质二次电池,其中,所述含氟环状碳酸酯的含量相对于所述非水溶剂的总体积为0.1体积%以上且30体积%以下。
3.根据权利要求1或2所述的非水电解质二次电池,其中,所述马来酰亚胺化合物的含量相对于所述非水电解质的总质量为0.1质量%以上且1.5质量%以下。
4.根据权利要求1~3中任一项所述的非水电解质二次电池,其中,所述环状羧酸酐的含量相对于所述非水电解质的总质量为0.1质量%以上且2.5质量%以下。
5.根据权利要求1~4中任一项所述的非水电解质二次电池,其中,所述马来酰亚胺化合物包含N-甲基马来酰亚胺、N-乙基马来酰亚胺、N-丙基马来酰亚胺、N-丁基马来酰亚胺、N-乙烯基马来酰亚胺或N-苯基马来酰亚胺中的至少任一种。
6.根据权利要求1~5中任一项所述的非水电解质二次电池,其中,所述环状羧酸酐包含二甘醇酐、甲基二甘醇酐、二甲基二甘醇酐、乙基二甘醇酐、甲氧基二甘醇酐、乙氧基二甘醇酐、乙烯基二甘醇酐、烯丙基二甘醇酐、二乙烯基二甘醇酐或二乙烯基二甘醇酐中的至少任一种。
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JP2016143536A (ja) * | 2015-01-30 | 2016-08-08 | 三菱化学株式会社 | 非水系電解質、及びそれを用いた非水系電解質二次電池 |
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JP2012234767A (ja) * | 2011-05-09 | 2012-11-29 | Sony Corp | 二次電池用電解液、二次電池、電子機器、電動工具、電動車両および電力貯蔵システム |
JP6098062B2 (ja) * | 2011-08-02 | 2017-03-22 | 三菱化学株式会社 | 非水系電解液及びそれを用いた非水系電解液二次電池 |
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JP2006156331A (ja) * | 2004-11-05 | 2006-06-15 | Sony Corp | 電池 |
US20070042267A1 (en) * | 2005-08-18 | 2007-02-22 | Samsung Sdi Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
CN101276936A (zh) * | 2007-03-28 | 2008-10-01 | 三洋电机株式会社 | 非水电解质二次电池 |
CN103811815A (zh) * | 2011-01-31 | 2014-05-21 | 三菱化学株式会社 | 非水电解液及使用该非水电解液的非水电解质二次电池 |
JP2016143536A (ja) * | 2015-01-30 | 2016-08-08 | 三菱化学株式会社 | 非水系電解質、及びそれを用いた非水系電解質二次電池 |
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