CN118281347A - Electrolyte, secondary battery and electronic device - Google Patents
Electrolyte, secondary battery and electronic device Download PDFInfo
- Publication number
- CN118281347A CN118281347A CN202410361655.5A CN202410361655A CN118281347A CN 118281347 A CN118281347 A CN 118281347A CN 202410361655 A CN202410361655 A CN 202410361655A CN 118281347 A CN118281347 A CN 118281347A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- nitrile solvent
- solvent
- nitrile
- 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
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 121
- 239000002904 solvent Substances 0.000 claims abstract description 116
- 150000002825 nitriles Chemical class 0.000 claims abstract description 81
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 150000005678 chain carbonates Chemical class 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- -1 2-dimethylpentyl Chemical group 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
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- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 241000720974 Protium Species 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 239000007769 metal material Substances 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
- 229920002401 polyacrylamide Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-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
- 230000009471 action Effects 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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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- 239000000460 chlorine Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 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
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- 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 230000008021 deposition Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 125000002347 octyl 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])[H] 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin 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
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052722 tritium Inorganic materials 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte, a secondary battery and an electronic device, wherein the electrolyte comprises: an organic solvent and an electrolyte salt, wherein the organic solvent comprises a nitrile solvent, and the ortho carbon atom of a cyano group in the nitrile solvent is a quaternary carbon atom. According to the application, the ortho-carbon atom of the cyano group in the nitrile solvent in the electrolyte is a quaternary carbon atom, and the nitrile solvent has higher stability relative to the battery cathode, so that the electrolyte can not only utilize the advantages of high dielectric constant, low viscosity and high flash point of the nitrile solvent, but also reduce the influence on the battery performance due to incompatibility of the nitrile solvent and the battery cathode.
Description
Technical Field
The application relates to the technical field of batteries, in particular to electrolyte, a secondary battery and electronic equipment.
Background
The nitrile solvent can meet the working voltage window of the positive electrode material of the main flow battery because of the high oxidation stable voltage. And the characteristics of high dielectric constant, low viscosity, high flash point and the like of the nitrile solvent ensure that an electrolyte system taking the nitrile solvent as a main solvent has the characteristics of high conductivity and high safety.
However, the nitrile solvent is very easy to react with the high-reducibility cathode in the battery, and the incompatibility between the cathode and the nitrile solvent is caused, so that the nitrile solvent is difficult to be used as the main solvent of the electrolyte at present and is generally added into the electrolyte in the form of an additive.
Thus, there is a need to overcome the problem of incompatibility of nitrile solvents with battery cathodes.
Disclosure of Invention
The application provides an electrolyte, a secondary battery and electronic equipment, wherein the electrolyte can effectively solve the problem that the nitrile solvent is incompatible with the negative electrode of the battery by selecting a special nitrile solvent.
In a first aspect, the present application provides an electrolyte comprising: an organic solvent and an electrolyte salt, wherein the organic solvent comprises a nitrile solvent, and the ortho carbon atom of a cyano group in the nitrile solvent is a quaternary carbon atom.
According to the application, the ortho-carbon atom of the cyano group in the nitrile solvent in the electrolyte is a quaternary carbon atom, and the nitrile solvent has higher stability relative to the battery cathode, so that the electrolyte can not only utilize the advantages of high dielectric constant, low viscosity and high flash point of the nitrile solvent, but also reduce the influence on the battery performance due to incompatibility of the nitrile solvent and the battery cathode.
In some embodiments, the nitrile solvent is present in the organic solvent in an amount of 5% by volume or more; optionally, the volume percentage of the nitrile solvent in the organic solvent is 10% -99%.
In some embodiments, the nitrile solvent comprises at least one of a mono-nitrile solvent, a di-nitrile solvent, or a tri-nitrile solvent; optionally, the nitrile solvent comprises a mono-nitrile solvent.
In some embodiments, the nitrile solvent comprises a compound of formula I,
Wherein R 1、R2、R3 is each independently represented as a substituent other than H.
In some embodiments, R 1、R2、R3 is each independently represented by at least one of a C1-C10 substituted or unsubstituted alkyl group, a C6-C30 substituted or unsubstituted aryl group, or a halogen atom; alternatively, R 1、R2、R3 is independently represented as a C1-C10 substituted or unsubstituted alkyl group; alternatively, R 1、R2、R3 is independently represented as a C1-C5 unsubstituted alkyl group.
In some embodiments, R 1、R2、R3 is each represented as methyl.
In some embodiments, the organic solvent further comprises at least one of a chain carbonate, a cyclic carbonate, an ether solvent; optionally, the organic solvent further comprises at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate, fluoroethylene carbonate and vinylene carbonate.
In some embodiments, the concentration of the electrolyte salt in the electrolyte is no greater than 2mol/L; optionally, the concentration of the electrolyte salt in the electrolyte is not greater than 1mol/L.
In a second aspect, the present application provides a secondary battery comprising the electrolyte according to any one of the embodiments of the first aspect.
In a third aspect, the present application provides an electronic device, including a secondary battery according to any one of the embodiments of the second aspect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
Fig. 1 is a graph of coulombic efficiency of a lithium copper half-cell tested with the electrolyte configured in example 1.
Fig. 2 is a graph of coulombic efficiency of a lithium copper half-cell tested with the electrolyte configured in comparative example 1.
Specific embodiments of the present application have been shown by way of the above drawings and will be described in more detail below. The drawings and the written description are not intended to limit the scope of the inventive concepts in any way, but rather to illustrate the inventive concepts to those skilled in the art by reference to the specific embodiments.
Detailed Description
Each example or embodiment in this specification is described in a progressive manner, each example focusing on differences from other examples.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The term "alkyl" encompasses both straight and branched chain alkyl groups. For example, the alkyl group may be a C5-C500 alkyl group, a C20-C400 alkyl group, a C1-C50 alkyl group, a C1-C40 alkyl group, a C1-C30 alkyl group, a C1-C20 alkyl group, a C1-C12 alkyl group, a C1-C10 alkyl group, a C1-C6 alkyl group, or a C1-C4 alkyl group. In some embodiments, alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, decyl and the like. In addition, the alkyl group may be optionally substituted. The term "substituted alkyl" refers to an alkyl group in which hydrogen atoms are partially or fully substituted with substituents, and the term "unsubstituted alkyl" refers to an alkyl group in which hydrogen atoms are fully unsubstituted with substituents. The term "halogen atom" refers to fluorine, chlorine, bromine, iodine, and the like.
The term "quaternary carbon atom" means that the carbon atom is not directly attached to a hydrogen atom.
The term "hydrogen" refers to 1H (protium, H), 2H (deuterium, D) or 3H (tritium, T). In various embodiments, the "hydrogen" may be 1H (protium, H).
Throughout this specification, substituents of a compound are disclosed in groups or ranges. It is expressly intended that such description include each individual subcombination of the members of these groups and ranges. For example, the term "C1-C10 substituted or unsubstituted alkyl" is expressly contemplated to disclose C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C1～C10、C1～C9、C1～C8、C1～C7、C1～C6、C1～C5、C1～C4、C1～C3、C1～C2、C2～C10、C2～C9、C2～C8、C2～C7、C2～C6、C2～C5、C2～C4、C2～C3、C3～C10、C3～C9、C3～C8、C3～C7、C3～C6、C3～C5、C3～C4、C4～C10、C4～C9、C4～C8、C4～C7、C4～C6、C4～C5、C5～C10、C5～C9、C5～C8、C5～C7、C5～C6、C6～C10、C6～C9、C6～C8、C6～C7、C7～C10、C7～C9、C7～C8、C8～C10、C8～C9 and C9-C10 substituted or unsubstituted alkyl groups separately.
As other examples, integers in the range 5-40 are specifically contemplated to disclose 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 individually; integers in the range of 1-20 are specifically contemplated as disclosing 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 individually. Accordingly, other groups or ranges are expressly contemplated.
In the present application, "nitrile solvent" means an organic compound containing an organic group cyano group and being liquid at normal temperature.
As described in the background art above, the nitrile solvent is incompatible with the battery negative electrode, so that the nitrile solvent cannot be used as the main solvent of the electrolyte, and the application of the nitrile solvent in the electrolyte is also affected, so that the problem of incompatibility of the battery negative electrode and the nitrile solvent needs to be improved.
For the above problems, in the related art, the concentration of electrolyte salt in the electrolyte is generally increased, and a large amount of components beneficial to forming a solid electrolyte membrane are added, so that a more stable solid electrolyte membrane is formed, the stability of the interface between the electrolyte and the anode is improved, the corrosion of the nitrile solvent to the anode is slowed down, and the problem that the anode and the nitrile solvent of the battery are incompatible is solved. However, the above method has problems in that the high electrolyte salt concentration and the addition of a large amount of film forming agent raise the viscosity of the electrolyte, resulting in a decrease in ionic conductivity of the electrolyte, and also in that the cost of the electrolyte is greatly increased, and the use of nitrile solvents in the electrolyte is also limited.
Based on the above, the application provides the electrolyte, and the problem that the battery cathode is incompatible with the nitrile solvent can be effectively solved by selecting the nitrile solvent with a specific structure, so that the adverse effect of the nitrile solvent on the battery performance can be reduced. Embodiments of the present application are described in detail below.
Electrolyte solution
In a first aspect, the present application provides an electrolyte comprising: and the organic solvent comprises a nitrile solvent, wherein the ortho-carbon atom of the cyano group in the nitrile solvent is a quaternary carbon atom.
According to the application, the ortho-carbon atom of the cyano group in the nitrile solvent in the electrolyte is a quaternary carbon atom, and the nitrile solvent has higher stability relative to the battery cathode, so that the electrolyte can not only utilize the advantages of high dielectric constant, low viscosity and high flash point of the nitrile solvent, but also reduce the influence on the battery performance due to incompatibility of the nitrile solvent and the battery cathode.
Specifically, the inventor has analyzed that the reason why the negative electrode of the battery in the nitrile solvent in the electrolyte is not compatible is mainly: the negative electrode of the battery shows stronger reducibility in the use process, mainly because substances such as lithium, sodium, lithium intercalation/sodium-carbon compounds and the like exist, cyano groups in the nitrile solvent are strong electron-withdrawing groups, and the strong electron-withdrawing effect of the cyano groups on adjacent carbon atoms can increase the activity of hydrogen atoms connected with the adjacent carbon atoms, so that the reaction with the reducing substances on the negative electrode of the battery is easier, the hydrogen atoms on the adjacent carbon atoms of the cyano groups in the nitrile solvent are removed, and further, the generation of gas (mainly hydrogen) is caused, and the process is accompanied with the consumption of active materials, so that the cycle performance and the charge performance of the battery are reduced, and further, if the nitrile solvent is excessively high in content in electrolyte, the safety accidents such as battery explosion and the like can be possibly caused.
Based on the above findings, the nitrile solvent with cyano group as the quaternary carbon atom is selected, and the quaternary carbon atom is not connected with hydrogen atom, so that the nitrile solvent does not contain hydrogen atom activated by cyano group, and the reaction is not easy to occur, thereby effectively improving the compatibility of the nitrile solvent and the battery cathode and reducing the adverse effect of the nitrile solvent on the battery performance.
In general, the nitrile solvent in the electrolyte does not only dissolve and ionize electrolyte salt, but also can participate in the formation of solid electrolyte membrane, and the electrolyte provided by the application does not require any further action, and the application mainly solves the problem that the nitrile solvent in the electrolyte is not compatible with the negative electrode of the battery.
In some embodiments, the nitrile solvent is present in the organic solvent in an amount of 5% by volume or more; optionally, the nitrile solvent accounts for 10-99% of the organic solvent by volume.
In some embodiments, the nitrile solvent has good compatibility with the battery cathode, so the addition amount of the nitrile solvent in the electrolyte can be unlimited, thereby improving the content of the nitrile solvent in the electrolyte, and when the volume percentage of the nitrile solvent in the organic solvent can be more than 5%, the advantages of high dielectric constant, low viscosity and high flash point of the nitrile solvent can be fully utilized, and the ionic conductivity and the safety performance of the electrolyte can be further improved. For example, the nitrile solvent may be present in the organic solvent in an amount ranging from 5%,10%,15%,20%,25%,30%,35%,40%,45%,50%,55%,60%,65%,70%,75%,80%,85%,90%,95%,99%,100%, or any combination thereof. Preferably, the nitrile solvent accounts for 10-99% of the organic solvent by volume, so that the electrolyte has better ionic conductivity and safety performance.
In some embodiments, the nitrile solvent comprises at least one of a mono-nitrile solvent, a di-nitrile solvent, or a tri-nitrile solvent.
In some embodiments, the nitrile solvent may include, but is not limited to, one cyano group, or may also include two or three cyano groups, and since adjacent carbon atoms of each cyano group are quaternary carbon atoms, the mono-nitrile solvent, the di-nitrile solvent or the tri-nitrile solvent has good compatibility with the battery anode, which can effectively reduce the influence of the nitrile solvent on the battery performance.
Further, the nitrile solvent includes a mono-nitrile solvent. The mono-nitrile solvent generally has a simpler structure and a relatively smaller molecular weight than the di-nitrile solvent or the tri-nitrile solvent, so that the viscosity is relatively smaller and the molecular polarity is relatively larger, thereby having better dissolution ionization performance for the electrolyte salt, being more beneficial to improving the ionic conductivity of the electrolyte, and further improving the performance of the battery. Meanwhile, the cost of the mono-nitrile solvent is relatively low, which is beneficial to reducing the cost of the electrolyte.
In some embodiments, the nitrile solvent comprises a compound of formula I,
Wherein R 1、R2、R3 is each independently represented as a substituent other than H.
In some embodiments, the compound shown in the formula I belongs to a mono-nitrile solvent, and the carbon atom adjacent to the cyano group does not contain unsaturated carbon-carbon bonds besides being connected with hydrogen atoms, so that the compound has relatively higher polarity, has better dissolution ionization effect on electrolyte salt, and can further improve the ionic conductivity of the electrolyte.
Further, R 1、R2、R3 is independently represented by at least one of a C1-C10 substituted or unsubstituted alkyl group, a C6-C30 substituted or unsubstituted aryl group, or a halogen atom. At the moment, the molecular weight of the nitrile solvent is relatively smaller, the viscosity is relatively smaller, the dissolution and ionization effects on electrolyte salt are better, and the ionic conductivity of the electrolyte can be further improved.
For example, the C1-C10 unsubstituted alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2, 3-dimethylpentyl, 2-dimethylpentyl, n-heptyl, 2-methylhexyl, 3-dimethylpentyl, 2, 4-dimethylpentyl, 3-ethylpentyl, 2, 3-trimethylbutyl and the like; the C1-C10 substituted alkyl group may include a C1-C10 fluoroalkyl group, and the C1-C10 fluoroalkyl group may include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-monofluoroethyl group, a1, 1-difluoroethyl group, a1, 1-trifluoroethyl group, a perfluoroethyl group, etc.; the C6-C30 substituted or unsubstituted aryl group includes aromatic compounds containing one to a plurality of benzene rings, the C6-C30 substituted aryl group may include a C6-C30 fluorinated aryl group, and the C6-C30 fluorinated aryl group may be monofluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorophenyl or the like.
Further, R 1、R2、R3 is independently represented as a C1-C10 substituted or unsubstituted alkyl group. At the moment, the molecular weight of the nitrile solvent is relatively smaller, the viscosity is relatively smaller, the dissolution and ionization effects on electrolyte salt are better, and the ionic conductivity of the electrolyte can be further improved.
Further, R 1、R2、R3 is independently represented by a C1-C5 unsubstituted alkyl group. Since the unsubstituted alkyl group is an electron donating group, when the hydrogen atom on the carbon atom adjacent to the cyano group is completely substituted with the unsubstituted alkyl group, the polarity of the nitrile solvent is larger at this time, and when R 1、R2、R3 is independently represented as a C1 to C5 unsubstituted alkyl group, the molecular weight of the nitrile solvent is smaller, the viscosity is smaller, the dissolution ionization effect on the electrolyte salt is better, and the ionic conductivity of the electrolyte solution can be further improved.
In some embodiments, R 1、R2、R3 is each represented as methyl. At the moment, the nitrile solvent has large polarity, small molecular weight and viscosity, has better dissolution and ionization effects on electrolyte salt, and can further improve the ionic conductivity of the electrolyte.
In some embodiments, the organic solvent further comprises at least one of a chain carbonate, a cyclic carbonate, an ether solvent.
In some embodiments, the performance of the battery can be further improved by the combination of other organic solvents and nitrile solvents, and the chain carbonic ester can participate in the formation of the solid electrolyte membrane, so that the stability of the interface between the electrolyte and the electrode is further improved; the cyclic carbonate can further improve the dissolution and ionization of the electrolyte salt by the solvent and improve the conductivity; the ether solvent can further reduce the viscosity of the electrolyte and improve the wettability of the electrolyte.
Further, the organic solvent further comprises at least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, fluoroethylene carbonate and vinylene carbonate. The electrolyte thus obtained can further improve the performance of the battery. It will be appreciated that some of the above-mentioned organic solvents may be used as film forming additives, i.e. some of the additives which are liquid at room temperature may be added as organic solvents, which may also include other solvents known in the art, and may be selected by those skilled in the art according to actual needs.
In some embodiments, the concentration of the electrolyte salt in the electrolyte is no greater than 2mol/L.
In some embodiments, the nitrile solvent and the battery cathode have good compatibility, so that no more electrolyte salt is needed to participate in the formation of the solid electrolyte membrane to improve the interface stability of the electrolyte and the electrode, thus the concentration of the electrolyte salt in the electrolyte can be properly reduced to reduce the viscosity of the electrolyte and save the cost of the electrolyte. For example, the concentration of the electrolyte salt in the electrolyte may be 2mol/L、1.8mol/L、1.6mol/L、1.5mol/L、1.4mol/L、1.2mol/L、1mol/L、0.8mol/L、0.6mol/L、0.5mol/L、0.4mol/L、0.2mol/L、0.1mol/L, or any of the values set forth above. Further, the concentration of the electrolyte salt in the electrolyte is not more than 1mol/L, and at this time, the viscosity of the electrolyte is lower and the cost is lower.
The kind of the electrolyte salt in the present application is not particularly limited, and the electrolyte salt may include a lithium salt or a sodium salt. As an example, the lithium salt includes, but is not limited to, at least one of LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liClO 4 (lithium perchlorate), liFSI (lithium bis-fluorosulfonimide), liTFSI (lithium bis-trifluoromethanesulfonyl imide), liTFS (lithium trifluoromethanesulfonate), litfob (lithium difluorooxalato borate), liBOB (lithium dioxaato borate), liPO 2F2 (lithium difluorophosphate), liDODFP (lithium difluorodioxaato phosphate), and LiOTFP (lithium tetrafluorooxalato phosphate). The lithium salts may be used singly or in combination of two or more. As an example, the sodium salt may be selected from at least one of NaPF 6、NaClO4、NaBCl4、NaSO3CF3 and Na (CH 3)C6H4SO3).
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
The electrolyte may be prepared according to a conventional method in the art. For example, the organic solvent, electrolyte salt, and optional additives may be uniformly mixed to obtain the electrolyte. The order of addition of the materials is not particularly limited, and for example, electrolyte salt and optional additives are added into an organic solvent and mixed uniformly to obtain an electrolyte; or adding electrolyte salt into the organic solvent, and then adding optional additives into the organic solvent to be uniformly mixed to obtain the electrolyte.
Secondary battery
In a second aspect, the present application provides a secondary battery comprising the electrolyte of any one of the embodiments of the first aspect.
According to the present application, since the secondary battery includes the electrolyte of any one of the embodiments of the first aspect, there is an advantageous effect of the first aspect.
In general, the secondary battery further includes a positive electrode tab, a negative electrode tab, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer comprises a positive active material.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode active material may employ a positive electrode active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of the olivine-structured lithium-containing phosphate may include, but are not limited to, at least one of lithium iron phosphate (e.g., liFePO 4 (also simply LFP)), a composite of lithium iron phosphate and carbon, a composite of lithium manganese phosphate (e.g., liMnPO 4), a composite of lithium manganese phosphate and carbon, a composite of lithium iron phosphate and manganese phosphate, and a composite of lithium manganese iron phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ Negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. The negative electrode active material may also be an alkali metal simple substance including, but not limited to, at least one of lithium metal, sodium metal. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ Isolation Membrane ]
In some embodiments, the present application is not particularly limited in the kind of the separator, and any known porous structure separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may be a lithium ion battery, a lithium metal battery, a sodium ion battery, or a sodium metal battery.
Electronic equipment
In a third aspect, the present application provides an electronic device comprising a secondary battery according to any one of the embodiments of the second aspect.
According to the present application, since the electronic device includes the secondary battery of any one of the embodiments of the second aspect, the electronic device has the advantageous effects of the second aspect.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable telephone, a portable facsimile machine, a portable copier, a portable printer, a headset, a video recorder, a liquid crystal television, a portable cleaner, a portable CD-player, a mini-compact disc, a transceiver, an electronic notepad, a calculator, a memory card, a portable audio recorder, a radio, a backup power source, a motor, an automobile, a motorcycle, a power assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flash light, a camera, a household large battery, a lithium ion capacitor, and the like.
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Electrolyte performance test:
Adopting 2032 button cell configuration and accessories, placing a positive electrode shell, a copper foil with the diameter of 19 mu m, electrolyte, a diaphragm, a lithium sheet with the diameter of 16 mu m, a gasket and a spring sheet in sequence, and assembling the button cell; and tested at a deposition capacity of 1mA/cm 2 current density, 0.5mAh/cm 2, and the coulombic efficiencies of the lithium copper batteries of the electrolytes configured in the examples and comparative examples were counted.
Example 1
Preparation of electrolyte: liFeSI is added into TMAN (trimethylacetonitrile) and FEC (fluoroethylene carbonate) solvents (for example, 1mL of solvent is prepared, the volumes of TMEA and FEC are respectively 0.9mL:0.1 mL) in a volume ratio of 9:1 according to a lithium salt concentration ratio of 1mol/L, and the mixed electrolyte is prepared after uniform stirring, so that the electrolyte is obtained.
The electrolyte was subjected to electrolyte performance test, and the coulombic efficiency of the lithium copper half cell tested using the electrolyte configured in example 1 is shown in fig. 1.
Comparative example 1
Preparation of electrolyte: slowly dissolving lithium hexafluorophosphate (LiPF 6) lithium salt in an organic carbonate solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a mass ratio of 3:7, so that the concentration of the lithium LiPF 6 lithium salt of the electrolyte is 1mol/L, and uniformly stirring to obtain the electrolyte.
The electrolyte was subjected to electrolyte performance test, and the coulombic efficiency of the lithium copper half cell tested using the electrolyte configured in comparative example 1 is shown in fig. 2.
As can be seen from fig. 1 and 2, under the same test conditions and battery configuration, the carbonate electrolyte of the conventional lithium ion battery cannot be compatible with the lithium metal battery, the coulomb efficiency of the lithium copper half-cell is only about 90%, and the battery performance shows steep jump after 20 cycles; the electrolyte prepared by using TMAN as a main solvent has good compatibility and cycle stability to metallic lithium, the coulombic efficiency of the battery is near 95% in 50 battery cycles, and the performance of the electrolyte is far superior to that of the conventional carbonate electrolyte.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. An electrolyte, comprising: an organic solvent and an electrolyte salt, wherein the organic solvent comprises a nitrile solvent, and the ortho carbon atom of a cyano group in the nitrile solvent is a quaternary carbon atom.
2. The electrolytic solution according to claim 1, wherein the nitrile solvent is contained in the organic solvent in an amount of 5% by volume or more;
optionally, the volume percentage of the nitrile solvent in the organic solvent is 10% -99%.
3. The electrolyte of claim 1, wherein the nitrile solvent comprises at least one of a mono-nitrile solvent, a di-nitrile solvent, or a tri-nitrile solvent;
optionally, the nitrile solvent comprises a mono-nitrile solvent.
4. The electrolyte of claim 3, wherein the nitrile solvent comprises a compound of formula I,
Wherein R 1、R2、R3 is each independently represented as a substituent other than H.
5. The electrolyte according to claim 4, wherein R 1、R2、R3 is independently represented by at least one of a C1 to C10 substituted or unsubstituted alkyl group, a C6 to C30 substituted or unsubstituted aromatic group, or a halogen atom;
alternatively, R 1、R2、R3 is independently represented as a C1-C10 substituted or unsubstituted alkyl group;
Alternatively, R 1、R2、R3 is independently represented as a C1-C5 unsubstituted alkyl group.
6. The electrolyte of claim 5 wherein R 1、R2、R3 is each represented as methyl.
7. The electrolytic solution according to any one of claims 1 to 6, wherein the organic solvent further comprises at least one of a chain carbonate, a cyclic carbonate, and an ether solvent;
Optionally, the organic solvent further comprises at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate, fluoroethylene carbonate and vinylene carbonate.
8. The electrolyte according to any one of claims 1 to 6, wherein the concentration of the electrolyte salt in the electrolyte is not more than 2mol/L;
optionally, the concentration of the electrolyte salt in the electrolyte is not greater than 1mol/L.
9. A secondary battery comprising the electrolyte according to any one of claims 1 to 8.
10. An electronic device comprising the secondary battery according to claim 9.
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