CN116487700A - Nonaqueous electrolyte and lithium ion battery - Google Patents
Nonaqueous electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN116487700A CN116487700A CN202310456114.6A CN202310456114A CN116487700A CN 116487700 A CN116487700 A CN 116487700A CN 202310456114 A CN202310456114 A CN 202310456114A CN 116487700 A CN116487700 A CN 116487700A
- Authority
- CN
- China
- Prior art keywords
- compound
- lithium
- positive electrode
- nonaqueous electrolyte
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 39
- -1 sulfonate compound Chemical class 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 229910006700 SnO2-Li4Ti5O12 Inorganic materials 0.000 claims description 9
- 229910006690 SnO2—Li4Ti5O12 Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- 229910020923 Sn-O Inorganic materials 0.000 claims description 3
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 claims description 3
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 abstract description 16
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000011241 protective layer Substances 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920005554 polynitrile Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000005555 sulfoximide group Chemical group 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
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- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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Abstract
In order to solve the problem of capacity attenuation of a battery caused by volume expansion generated in a long-term cyclic charge-discharge process of a lithium ion battery in the prior art, the invention provides a non-aqueous electrolyte which comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a compound A, and the structure of the compound A is as follows:wherein R is 1 ～R 4 One or more selected from H, F, alkoxy hydrocarbon groups of 1 to 20 carbon atoms and alkane groups of 1 to 20 carbon atoms. Meanwhile, the invention also discloses a lithium ion battery comprising the nonaqueous electrolyte. The non-aqueous electrolyte provided by the invention comprises a compound A, wherein the compound A can be fully and effectively complexed with transition metal of a positive electrode to form a protective layer on the surface of the positive electrode, and can be subjected to polymerization reaction after ring opening to form a net structure, and the net structure is attached to the surface of the positive electrode to form a positive electrodeThe dense protective film can prevent electrolyte from entering the material to damage the material, so that the lithium battery can be effectively protected.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a non-aqueous electrolyte and a lithium ion battery.
Background
The lithium ion battery is widely applied to the fields of digital codes, electric tools, aerospace, energy storage, power automobiles and the like due to the advantages of high specific energy, no memory effect, long cycle life and the like, and the rapid development of electronic information technology and consumer products brings higher requirements to the high voltage and high energy density energy of the lithium ion battery; in application, the high-voltage positive electrode material is widely applied to portable electronic equipment such as mobile phones, notebook computers and the like and large-scale energy storage devices of electric vehicles due to the advantages of high energy density, environmental friendliness, long cycle life and the like.
However, as the limiting voltage of the positive electrode material is continuously increased, the high-temperature performance of the battery is seriously deteriorated while the gram capacity of the battery material is increased, the long cycle life cannot be ensured, especially, the volume of the material is expanded and serious cracks are caused in the long-term cycle charge and discharge process under high voltage (more than 4.5V), and the solvent in the electrolyte enters the inside of the positive electrode material to destroy the structure, so that the problem of serious capacity attenuation is finally caused.
Disclosure of Invention
Aiming at the problem of battery capacity attenuation caused by volume expansion generated in the long-term cyclic charge-discharge process of a lithium ion battery in the prior art, the non-aqueous electrolyte and the lithium ion battery are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the present invention provides a nonaqueous electrolyte comprising an organic solvent, a lithium salt, and an additive comprising a compound a having the structure shown below:
wherein R is 1 ～R 4 One or more selected from H, F, alkoxy hydrocarbon groups of 1 to 20 carbon atoms and alkane groups of 1 to 20 carbon atoms.
Optionally, the compound a is selected from one or more of the following compounds:
optionally, the compound B also comprises a compound B, wherein the structural general formula of the compound B is shown as follows:
wherein R is 5 Li, na, K, rb and Cs.
Optionally, the compound B is selected from one or more of the following compounds:
optionally, the mass percentage of the compound A is 0.5% -10% based on 100% of the total mass of the nonaqueous electrolyte.
Optionally, the mass percentage of the compound B is 0.5% -10% based on 100% of the total mass of the nonaqueous electrolyte.
Optionally, the additive further comprises one or more of sulfonate compounds, fluorocarbons and nitrile compounds; the organic solvent comprises two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
Optionally, the lithium salt includes a compound of fluorine-containing element and lithium element.
In another aspect, the present invention provides a lithium ion battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte as described above.
Optionally, the positive electrode comprises a positive electrode active material, wherein the positive electrode active material is selected from one or more of lithium cobaltate, lithium nickel manganese cobalt ternary material, lithium iron phosphate and lithium manganateSeed; the anode comprises an anode active material selected from the group consisting of graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composites, li-Sn alloys, li-Al alloys, li-Sn-O alloys, sn, snO, snO2, and TiO 2 -Li 4 Ti 5 O 12 One or more of the following.
The non-aqueous electrolyte provided by the invention comprises the compound A, wherein the compound A is a polynitrile functional group compound, and compared with other traditional nitrile compounds, the compound A contains a large number of nitrile functional groups, can be fully and effectively complexed with transition metal of a positive electrode, forms a protective layer on the surface of the positive electrode, can perform polymerization reaction after ring opening to form a reticular structure, is attached to the surface of the positive electrode, forms a layer of compact protective film on the surface of the positive electrode, and can prevent the electrolyte from entering the material to damage the material, thereby protecting the lithium battery more effectively.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
The invention provides a nonaqueous electrolyte, which comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a compound A, and the structure of the compound A is shown as follows:
wherein R is 1 ～R 4 One or more selected from H, F, alkoxy hydrocarbon groups of 1 to 20 carbon atoms and alkane groups of 1 to 20 carbon atoms.
Specifically, when said R 1 ～R 4 When each is independently selected from C1-20 alkyl groups, the alkyl groups may beThe chain hydrocarbon group includes a straight chain group and a branched chain group, and the cyclic group may have a substituent or may not have a substituent; in preferred embodiments the alkyl groups include one or more of ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopentyl, dimethylbutyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, isohexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 1, 2-trimethylpropyl, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, isoheptyl, cycloheptyl, n-octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
In some embodiments, the compound a is selected from one or more of the following compounds:
specifically, in a more preferred embodiment the compound A is 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinodimethane (CAS: 29261-33-4) having the following structure:
in some embodiments, compound B is also included, the compound B having the general structural formula:
wherein R is 5 Li, na, K, rb and Cs.
The compound B in the electrolyte contains a fluorine-containing sulfoximine anion group, negative charges on the fluorine-containing sulfoximine anion are highly dispersed under the conjugated delocalization of the sulfoximine group and the strong electron-withdrawing action of the fluorine-containing group, and a layer of stable passivation film can be formed, so that the anions generally show stronger oxidation resistance and the oxidation resistance of the electrolyte can be improved; the compound B and the polynitrile compound A cooperate to jointly prevent the electrolyte from corroding the positive electrode active material, so that the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery are maintained and improved.
In some embodiments, the compound B is selected from one or more of the following compounds:
specifically, in some preferred embodiments, the compound B is a lithium bis-fluorosulfonyl imide salt (CAS: 171611-11-3) having the structure:
the lithium difluorosulfimide has high stability (no decomposition below 200 ℃), excellent low-temperature performance and good hydrolytic stability, and can effectively reduce the high-low temperature resistance of an SEI layer formed on the surface of an electrode at low temperature and reduce the capacity loss of a lithium battery in the placing process when being used as an electrolyte additive of the lithium ion battery, thereby providing high battery capacity and electrochemical performance of the battery.
In some embodiments, the mass percentage of the compound a is 0.5% to 10% based on 100% of the total mass of the nonaqueous electrolytic solution.
In some embodiments, the mass percentage of the compound B is 0.5% to 10% based on 100% of the total mass of the nonaqueous electrolytic solution.
In some embodiments, the additive further comprises one or more of a sulfonate compound, a fluorocarbonate, and a nitrile compound; the organic solvent comprises two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
Specifically, in a preferred embodiment the sulfonate compound is 1, 3-Propane Sultone (PS), and the fluorocarbonate is fluoroethylene carbonate (FEC); the nitrile compounds include one or more of Succinonitrile (SN), adiponitrile (ADN), and 1,3,6 Hexanetrinitrile (HTCN).
In some embodiments, the lithium salt includes a compound of a fluorine-containing element and a lithium element.
The lithium salt comprises one or more of hexafluorophosphate, hexafluoroarsenate, perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl and lithium difluoroimide sulfonate; the concentration of lithium salt in the electrolyte is preferably 0.5-1.5M, if the concentration of lithium salt is too low, the conductivity of the electrolyte is affected, the multiplying power and the cycle performance of the whole battery system are reduced, and if the concentration of lithium salt is too high, the viscosity of the electrolyte is too high, the multiplying power of the battery system is also affected, and further preferably, the concentration of lithium salt is 0.8-1.3M.
Another embodiment of the present invention provides a lithium ion battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte as described above.
In some embodiments, the positive electrode comprises a positive electrode active material selected from one or more of lithium cobaltate, lithium nickel manganese cobalt ternary material, lithium iron phosphate, and lithium manganate; the anode comprises an anode active material selected from graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Al alloy, li-Sn-O alloy, sn, snO, snO 2 And TiO 2 -Li 4 Ti 5 O 12 One or more of the following.
The positive electrode also comprises a positive electrode current collector for leading out current, and the positive electrode active material is covered on the positive electrode current collector; the negative electrode also comprises a negative electrode current collector for leading out current, and the negative electrode active material is covered on the negative electrode current collector.
The invention is further illustrated by the following examples.
Example 1
The embodiment is used for explaining the nonaqueous electrolyte and lithium ions disclosed by the invention, and comprises the following steps:
preparation of electrolyte:
ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) are mixed according to the mass ratio of EC: PC: DEC: pp=1: 1:2:6, then adding additive PS, FEC, SN, AND and HTCN, mixing uniformly, adding lithium hexafluorophosphate (LiPF 6 ) A mixed solution having a molar concentration of 1.1mol/L was obtained, and compound A (CAS: 29261-33-4) and compound B (CAS: 171611-11-3) was added to the mixed solution, and the other components shown in example 1 of Table 1 in mass percent were added to obtain a nonaqueous electrolytic solution.
Preparation of a positive plate:
the positive electrode active material lithium cobaltate and the conductive agent CNT are mixed, and the binder polyvinylidene fluoride is prepared by the following components in weight 97:1.5:1.5 uniformly stirring and mixing in an N-methyl pyrrolidone solvent to form positive electrode slurry, coating the slurry on a positive electrode current collector aluminum foil, drying and cold pressing to obtain a positive electrode plate.
Preparing a negative plate:
the negative electrode active material graphite, the conductive agent acetylene black, the adhesive styrene-butadiene rubber and the thickener sodium carboxymethyl cellulose are mixed according to the mass ratio of 95:2:2: and 1, uniformly stirring and mixing the mixture in a proper amount of deionized water solvent to form negative electrode slurry, coating the slurry on a negative electrode current collector copper foil, and drying and cold pressing the negative electrode slurry to obtain a negative electrode plate.
Preparing a lithium ion battery:
and stacking the positive plate, the diaphragm and the negative plate in sequence, enabling the diaphragm to be positioned between the positive plate and the negative plate, winding to obtain a bare cell, placing the bare cell into an outer packaging bag, drying, injecting the electrolyte, and performing procedures such as vacuum packaging, standing, formation, shaping and the like to complete the preparation of the lithium ion battery.
Examples 2 to 4
Examples are provided to illustrate the non-aqueous electrolyte and lithium ions disclosed herein, including most of the steps described in example 1, with the following differences:
the components in the nonaqueous electrolytic solution were added in the mass percentages shown in examples 2 to 4 of Table 1.
Examples 5 to 10
This example is for illustrating a nonaqueous electrolyte and lithium ions disclosed in the present invention, and includes most of the operation steps in example 1, which are different in that:
in the preparation of the nonaqueous electrolyte, the compound B was not added, and other components were added in the mass percentages shown in examples 5 to 10 of Table 1.
Comparative example 1
This comparative example is a comparative illustration of a nonaqueous electrolyte and lithium ions disclosed in the present invention, and includes most of the operation steps of example 1, which are different in that:
in the preparation of the nonaqueous electrolytic solution, the compound a and the compound B are not added.
Comparative examples 2 to 4
This example is a comparative illustration of a nonaqueous electrolyte and lithium ions disclosed herein, and includes a majority of the steps of example 1, which differ in that:
in the preparation of the nonaqueous electrolyte, the compound A was not added, and the other components were added in the mass percentages shown in comparative examples 2 to 4 in Table 1.
Performance testing
The following performance tests were performed on examples 1 to 10 and comparative examples 1 to 4 prepared as described above:
high temperature cycle testing of batteries
The testing method comprises the following steps: and placing the battery in an environment of 45+/-2 ℃, and calculating the capacity retention rate of the battery after circulation according to standard charge-discharge circulation, circulation multiplying power of 1C and charging voltage of 3.0-4.5V. The calculation formula is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity)/(first cycle discharge capacity) ×100%.
High temperature storage test of battery:
the testing method comprises the following steps: and (3) charging the battery core with the separated capacity to 4.5V at normal temperature with a current of 0.5C, placing the full-charge battery in an environment of 85 ℃ for 6 hours, thermally measuring the thickness expansion rate, discharging to 3.0V with a current of 0.5C after the battery core is recovered to room temperature, and recording the discharge capacity.
The test results obtained are filled in table 2.
TABLE 1
TABLE 2
As can be seen from the test results of table 2, the high temperature cycle, high temperature storage performance and expansion ratio of examples 1 to 4 are excellent overall, and the capacity retention ratio is highest, the thickness expansion ratio is lowest and the high temperature storage resistance is best in example 1 at each cycle; in examples 5 to 10, when only compound a was added, the capacity retention rate and high-temperature cycle performance of example 7 were best, i.e., the optimum amount of compound a added was 1%.
The test results of comparative examples 1 to 4 and comparative examples 2 to 4 revealed that examples 1 to 4 were higher in capacity retention rate and small in thickness expansion rate, and that comparative examples 2 to 4 were inferior in test results; comparative example 1, which does not include compound a, has poor high temperature cycle and high temperature storage properties as tested, as compared to examples 5 to 10; namely, a proper amount of the compound A disclosed by the invention is added into electrolyte to be fully and effectively complexed with transition metal of the positive electrode, a protective layer is formed on the surface of the positive electrode, and the protective layer is attached to the surface of the positive electrode, so that the electrolyte can be prevented from entering the inside of a material to damage the material, and a lithium battery can be effectively protected; in addition, the compound A and the compound B are obtained from the test data and added into the electrolyte at the same time to play a synergistic effect, a compact protective film is formed on the surface of the positive electrode, the electrolyte is prevented from entering the positive electrode active material layer to corrode the positive electrode active material, and then the high-temperature cycle performance and the storage performance of the battery are improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A nonaqueous electrolyte, comprising an organic solvent, a lithium salt and an additive, wherein the additive comprises a compound a, and the compound a has the structure shown as follows:
wherein R is 1 ～R 4 One or more selected from H, F, alkoxy hydrocarbon groups of 1 to 20 carbon atoms and alkane groups of 1 to 20 carbon atoms.
2. The non-aqueous electrolyte according to claim 1, wherein the compound a is selected from one or more of the following:
3. the non-aqueous electrolyte according to claim 1, further comprising a compound B having the structural formula:
wherein R is 5 Li, na, K, rb and Cs.
4. A non-aqueous electrolyte according to claim 3, wherein the compound B is selected from one or more of the following compounds:
5. the nonaqueous electrolyte according to claim 1, wherein the mass percentage of the compound a is 0.5% to 10% based on 100% of the total mass of the nonaqueous electrolyte.
6. The nonaqueous electrolyte according to claim 3, wherein the mass percentage of the compound B is 0.5% to 10% based on 100% of the total mass of the nonaqueous electrolyte.
7. The non-aqueous electrolyte according to claim 1, wherein the additive further comprises one or more of a sulfonate compound, a fluorocarbonate and a nitrile compound; the organic solvent comprises two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
8. The nonaqueous electrolytic solution according to claim 1, wherein the lithium salt comprises a compound containing a fluorine element and a lithium element.
9. A lithium ion battery comprising a positive electrode, a negative electrode, and the nonaqueous electrolyte according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode comprises a positive electrode active material selected from one or more of lithium cobaltate, lithium nickel manganese cobalt ternary material, lithium iron phosphate, and lithium manganate; the negative electrode comprises a negative electrode active material selected from graphite and mesophase micro-carbonBalls, hard carbon, soft carbon, silicon-carbon composites, li-Sn alloys, li-Al alloys, li-Sn-O alloys, sn, snO, snO 2 And TiO 2 -Li 4 Ti 5 O 12 One or more of the following.
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