CN111106386A - An electrolyte and lithium-ion battery - Google Patents
An electrolyte and lithium-ion battery Download PDFInfo
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- CN111106386A CN111106386A CN201911374339.7A CN201911374339A CN111106386A CN 111106386 A CN111106386 A CN 111106386A CN 201911374339 A CN201911374339 A CN 201911374339A CN 111106386 A CN111106386 A CN 111106386A
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- Prior art keywords
- electrolyte
- lithium
- group
- lithium salt
- additive
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- -1 hydrazone compound Chemical class 0.000 claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 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 claims description 2
- QVXQYMZVJNYDNG-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Li+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F QVXQYMZVJNYDNG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002981 polyvinylidene fluoride 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
- 238000010998 test method Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 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 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 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
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 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
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006256 anode slurry Substances 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 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
- 238000002955 isolation Methods 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 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
- 229910021382 natural graphite Inorganic materials 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
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 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
- 229920006254 polymer film Polymers 0.000 description 1
- 238000005086 pumping Methods 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
- 238000007493 shaping process Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 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
- 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
- 239000002562 thickening agent Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte and a lithium ion battery, which comprise electrolyte lithium salt, an organic solvent and an additive, wherein the additive comprises a hydrazone compound, and the structural formula of the hydrazone compound is as follows:
wherein X, Y, Z are each independently selected from C1～20Alkyl or C6～26Aryl group of (1). The electrolyte can be applied to lithium ion batteries, wherein the hydrazone compound as the additive can form a stable passive film on positive and negative electrodes, so that the exposure of active sites is reduced, and the high-temperature storage and cycle performance of the battery is improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte and a lithium ion battery.
Background
Compared with other batteries, the lithium ion battery has the advantages of light weight, small volume, high energy density, long cycle life, small self-discharge and the like, is widely applied to portable equipment such as smart phones, cameras, notebook computers and the like, and is rapidly popularized and applied in novel fields such as electric vehicles, large-scale energy storage devices and the like. With the wide application of lithium ion batteries, the temperature adaptability and safety performance of the lithium ion batteries become an important index of the lithium ion batteries. The stability of a lithium ion battery is influenced by many factors, wherein the electrolyte, as an important component of the lithium ion battery, has a great influence on the environmental suitability and safety performance of the lithium ion battery. The lithium ion battery electrolyte which is currently put into practical use is a non-aqueous electrolyte added with a traditional film-forming additive such as vinylene carbonate (abbreviated as VC) or fluoroethylene carbonate (abbreviated as FEC), and the excellent cycle performance of the battery is ensured by the addition of the VC and the FEC. However, VC has poor high-voltage stability, and FEC is easily decomposed to generate gas at high temperature. Therefore, under high voltage and high temperature conditions, it is difficult for these additives to meet the performance requirements of high temperature cycling.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the electrolyte and the lithium ion battery are provided, and the electrolyte can be applied to the preparation of the lithium ion battery, can form a stable passive film on a positive electrode and a negative electrode, reduces the exposure of active sites, and improves the high-temperature storage and cycle performance of the battery.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided an electrolyte comprising an electrolytic lithium salt, an organic solvent, and an additive comprising a hydrazone compound; the hydrazone compound has a structural formula as follows:
wherein X, Y, Z are each independently selected from C1～20Alkyl or C6～26Aryl group of (1).
In the above hydrazone compound, X, Y and Z may be different from each other or the same as each other in the structural formula.
When X, Y and Z are each independently selected from C1～20The specific type of the alkyl group is not particularly limited, and can be selected according to practical requirements, for example, the chain alkyl group and the cyclic alkyl group can be selected, wherein the chain alkyl group includes linear alkyl group and branched alkyl groupThe cyclic alkyl group may have a substituent or may not have a substituent. In the alkyl group, the lower limit of the number of carbon atoms in the alkyl group is preferably 1,3, 5, and the upper limit of the number of carbon atoms in the alkyl group is preferably 3, 4, 5, 6, 7, 8, 10, 12, 16.
Specifically, C1～20The alkyl group of (A) may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a cyclopentyl group, a 2, 2-dimethylpropyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a n-hexyl group, an isohexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1, 1, 2-trimethylpropyl group, a 3, 3-dimethylbutyl group, a n-heptyl group, a 2-heptyl group, a 3-heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhex, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicosyl.
When X, Y and Z are each independently selected from C6～26The aryl group of (b) is not particularly limited, and may be selected according to practical requirements, for example: the aryl group containing at least one phenyl group can be a biphenyl group or a condensed ring aromatic hydrocarbon group, other substituent groups can be connected to the biphenyl group and the condensed ring aromatic hydrocarbon group, the upper limit value of the number of carbon atoms in the aryl group is preferably 7, 8, 9, 10, 12, 14, 16, 18, 20 and 22, and the lower limit value of the number of carbon atoms in the aryl group is preferably 6, 7, 8 and 9.
Specifically, C6～26The aryl group of (B) may specifically be a phenyl group, a benzyl group, a biphenyl group, a p-tolyl group, an o-tolyl group, an m-tolyl group, a p-ethylphenyl group, an m-ethylphenyl group, an o-ethylphenyl group, a 3, 5-xylyl group, a 2, 6-dimethylphenyl group, a 3, 5-diethylphenyl group, a 2, 6-diethylphenyl group, a 3, 5-diisopropylphenyl group, a 2, 6-diisopropylphenyl group, a 3, 5-di-n-propylphenyl group, a 2, 6-di-n-propylphenyl group, a 3, 5-di-n-butylphenyl group, a 2, 6-di-n-butylphenyl group, a 3, 5-di-Phenyl, 3, 5-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, trityl, 1-naphthyl or 2-naphthyl.
According to some embodiments of the invention, X, Y, Z are each independently selected from C1～10Alkyl or C6～16Aryl group of (1).
According to some embodiments of the invention, X, Y, Z are each independently selected from C1～6Chain alkyl group of (1), C3～8Or C is a cyclic alkyl group6～9Aryl group of (1).
According to some embodiments of the invention, the additive is present in the electrolyte in an amount of 0.5 to 10% by weight.
According to some embodiments of the invention, the electrolytic lithium salt is an organic lithium salt or an inorganic lithium salt.
According to some embodiments of the invention, the electrolytic lithium salt is selected from a lithium salt of a fluorine-containing element or a lithium element.
According to some embodiments of the invention, the electrolyte lithium salt may be selected from at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide.
According to some embodiments of the invention, the concentration of the electrolyte lithium salt in the electrolyte solution is 0.5 to 2 mol/L. The electrolyte lithium salt concentration is too low, the conductivity of the electrolyte is low, and the multiplying power and the cycle performance of the whole battery system can be influenced; the concentration of the electrolyte lithium salt is too high, the viscosity of the electrolyte is too high, and the multiplying power of the whole battery system is also influenced. Preferably, the concentration of the electrolyte lithium salt in the electrolyte is 0.9-1.3 mol/L.
According to some embodiments of the present invention, the organic solvent is an organic complex solvent, and may be specifically selected from at least two of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), methyl formate, ethyl propionate, Propyl Propionate (PP), methyl butyrate, and tetrahydrofuran.
In a second aspect of the invention, there is provided a lithium ion battery comprising any one of the electrolytes provided in the first aspect of the invention. Specifically, the lithium ion battery includes a positive electrode sheet, a negative electrode sheet, a separator disposed between the positive electrode sheet and the negative electrode sheet, and an electrolyte.
The positive plate comprises a positive current collector and a positive active material layer positioned on the positive current collector. The material of the positive electrode active material layer generally includes a positive electrode active material, a conductive agent, and a binder; the positive electrode active material can be selected from lithium cobaltate (LiCoO)2) Lithium nickel manganese cobalt ternary material, lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) At least one of (1).
The negative plate comprises a negative current collector and a negative active material layer arranged on the negative current collector. The material of the negative active material layer generally includes a negative active material selected from natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, and the like, a conductive agent, and a binder2Spinel-structured lithiated TiO2-Li4Ti5O12And Li-Al alloy.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides an electrolyte, which comprises an additive hydrazone compound, wherein the hydrazone compound can form a stable passivation film on the positive and negative electrodes of a battery, effectively complex metal ions in a system, further stabilize the system, and improve the cycle performance and the storage performance of the battery at high temperature.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below.
FIG. 1 is a variation curve of the cycle capacity retention rate of batteries C1#, C2#, C7#45 ℃ along with the cycle;
FIG. 2 is a graph showing the thermal state thickness expansion of the cells C1#, C2#, and C7# as a function of time at 60 ℃.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Preparation of electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) were mixed in a mass ratio of 1:1:1, and the mixture was uniformly mixed to obtain an organic solvent. Then adding different additives (specifically according to table 1), mixing uniformly, adding lithium hexafluorophosphate (LiPF)6) The required mass of lithium hexafluorophosphate was calculated from the concentration of lithium salt of 1.1mol/L, and 7 kinds of comparative example electrolytes L1# -L2 # and example electrolytes L3# -L7 # were obtained by stirring them uniformly, and stored in a sealed state at room temperature for later use. The mass percentages of the components of the additive in the electrolyte are given in table 1; wherein PS is 1, 3-propane sultone, and VC is vinylene carbonate.
TABLE 1 additive and its content in comparative and example electrolytes
Preparation of (II) lithium ion battery
(1) Preparing a positive plate: the positive electrode active material lithium cobaltate (LiCoO)2) The conductive agent Carbon Nano Tube (CNT) and the adhesive polyvinylidene fluoride (PVDF) are fully stirred and mixed in N-methyl pyrrolidone (NMP) solvent according to the weight ratio of 97:1.5:1.5 to form uniform anode slurry; and coating the slurry on an Al foil of a positive current collector, drying and cold pressing to obtain the positive plate.
(2) Preparing a negative plate: fully stirring and mixing a negative active material graphite, a conductive agent acetylene black, a binder Styrene Butadiene Rubber (SBR), a thickening agent carboxymethyl cellulose sodium salt (CMC) and deionized water solvent according to a weight ratio of 95:2:2:1 to form uniform negative electrode slurry; and coating the slurry on a Cu foil of a negative current collector, drying and cold pressing to obtain the negative plate.
(3) Assembling: the method comprises the steps of stacking a positive plate, a diaphragm (a PE porous polymer film) and a negative plate in sequence, arranging the diaphragm between the positive plate and the negative plate to play a role in isolation, then winding to form a bare cell, then placing the bare cell into an outer packaging bag, respectively injecting the prepared electrolyte solution L1-L7 into a dried battery, then performing vacuum-pumping packaging, standing, formation, shaping and other processes, and correspondingly preparing the lithium ion battery C1-C7.
Specifically, the lithium ion batteries C1# to C7# prepared by the method and the corresponding proportion and the electrolyte of the embodiment have no difference in other aspects except that the additives are different.
(III) testing of cycle Performance and storage Performance of the Battery
And respectively testing the cycle performance and the storage performance of the lithium ion battery C1-C7 #.
The specific test method of the cycle performance comprises the following steps: after being placed at 45 +/-2 ℃ for 2 hours, calculating the capacity retention rate of the battery after circulation according to the following formula, wherein the standard charge-discharge cycle is 1C in cycle multiplying power and 3.0-4.4V in charging voltage:
the nth cycle capacity retention rate (%) (nth cycle discharge capacity)/(first cycle discharge capacity) × 100%;
the specific test method of the storage performance comprises the following steps: taking 2 sample batteries in each group at room temperature, testing the thickness of the battery core, placing the batteries at 60 +/-2 ℃ after the batteries are fully filled according to the standard, taking out the batteries at regular time to test the thermal state thickness, taking out the batteries which are 10% higher than the thermal state thickness from a box, taking out the batteries for 30 days at the longest, and calculating the expansion rate of the battery core according to the following formula:
and (3) the thickness expansion (%) of the nth day is (the thermal state thickness of the core of the nth day-the thickness of the core before boxing)/(the thickness of the core before boxing) × 100%.
The battery cycle performance and storage performance tests were performed by the above methods, and the obtained results are shown in fig. 1 to 2 and table 2.
TABLE 2 Battery cycling and storage Performance test results
As can be seen from tables 1 and 2 and FIGS. 1 to 2, the hydrazone compound as an additive is not added to the electrolyte of the comparative example cell C1# and the comparative example cell C2#, so that the cycle performance and the storage performance of the battery are poor, and compared with the comparative example cell C1# and the comparative example cell C2#, the hydrazone compounds of the example cells C3# to C7# are added to the electrolyte of the example cells C3# to C7#, so that the cycle performance and the storage performance of the battery are improved to different degrees; the performance test results of the battery C5# in the comparative example and the battery in the comparative example show that the hydrazone compound as the additive in the battery electrolyte is not too low, the concentration of the added hydrazone compound is not high enough to form films on positive and negative electrodes, and the complexation with transition metal ions is not good; as can be seen from the results of the performance tests of the example cell C3# and the example cell C6#, when the concentration of the hydrazone compound as the additive reaches a proper concentration, the cycle performance and the storage performance of the cell are obviously improved, and the significance is not great if the cycle performance and the storage performance are continuously improved.
Claims (10)
1. An electrolytic solution, comprising an electrolytic lithium salt, an organic solvent, and an additive, wherein the additive comprises a hydrazone compound; the hydrazone compound has a structural formula as follows:
wherein X, Y, Z are each independently selected from C1～20Alkyl or C6～26Aryl group of (1).
2. The electrolyte of claim 1, wherein X, Y, Z are each independently selected from C1～10Alkyl or C6～16Aryl group of (1).
3. The electrolyte of claim 2, wherein X, Y, Z are each independently selected from C1～6Chain alkyl group of (1), C3～8Or C is a cyclic alkyl group6～9Aryl group of (1).
4. The electrolyte of claim 1, wherein the additive is present in the electrolyte in an amount of 0.5 to 10% by weight.
5. The electrolyte of claim 1, wherein the electrolytic lithium salt is an organic lithium salt or an inorganic lithium salt.
6. The electrolyte of claim 5, wherein the electrolytic lithium salt is selected from a lithium salt of a fluorine-containing element or a lithium element.
7. The electrolyte of claim 6, wherein the electrolyte lithium salt is selected from at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, and lithium tris (trifluoromethylsulfonyl) methide.
8. The electrolyte according to claim 5, wherein the concentration of the electrolyte lithium salt in the electrolyte is 0.5 to 2 mol/L.
9. The electrolyte of any one of claims 1 to 8, wherein the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, tetrahydrofuran.
10. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator provided between the positive electrode sheet and the negative electrode sheet, and the electrolyte solution according to any one of claims 1 to 9.
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