CN117013078A - Electrolyte additive, electrolyte and lithium ion battery - Google Patents
Electrolyte additive, electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN117013078A CN117013078A CN202311116108.2A CN202311116108A CN117013078A CN 117013078 A CN117013078 A CN 117013078A CN 202311116108 A CN202311116108 A CN 202311116108A CN 117013078 A CN117013078 A CN 117013078A
- Authority
- CN
- China
- Prior art keywords
- additive
- electrolyte
- positive electrode
- ltoreq
- anode
- 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 64
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 80
- 230000000996 additive effect Effects 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- -1 sulfonate compound Chemical class 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002367 halogens Chemical group 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 33
- 239000007774 positive electrode material Substances 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 125000000524 functional group Chemical group 0.000 abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229910001428 transition metal ion Inorganic materials 0.000 description 8
- 239000006183 anode active material Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002879 Lewis base Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013538 functional additive Substances 0.000 description 4
- 150000007527 lewis bases Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 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 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 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
- 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- WHULDTBQXVKIHX-UHFFFAOYSA-N propan-2-yl cyanate Chemical compound CC(C)OC#N WHULDTBQXVKIHX-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The application relates to an electrolyte additive, electrolyte and a lithium ion battery. The electrolyte additive comprises a first additive, the first additive can be oxidized in preference to an electrolyte solvent in a first formation stage, and an oxidation product of the first additive is subjected to electropolymerization on the surface of the positive electrode, so that direct contact between the electrolyte and a positive electrode material is effectively isolated, oxidation of a positive electrode protection film under high voltage can be prevented, and the stability of the positive electrode protection film is improved; and because the tetramethyl silane group can remove water, the electrolyte solvent can be subjected to reduction reaction in the anode preferentially, the reduction of the anode protective film under high voltage can be prevented, and the stability of the anode protective film is improved. The S-containing heterocyclic functional group of the first additive can be combined with Li+ in the system, and the generated lithium-rich compound is favorable for the transmission of ions in the electrolyte and accelerates the formation of a stable lithium ion battery system. According to the scheme provided by the application, a stable protective film can be formed on the anode and the cathode, and the high-temperature cycle performance of the lithium ion battery is improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to an electrolyte additive, an electrolyte and a lithium ion battery.
Background
The lithium ion battery is widely applied to the fields of 3C digital codes, electric tools, aerospace, energy storage, power automobiles and the like due to the advantages of high specific energy, no memory effect, long cycle life and the like, and the rapid development of electronic information technology and consumer products puts higher demands on the high voltage and high energy density of the lithium ion battery. In lithium ion batteries, high-voltage positive electrode materials are widely applied to portable electronic equipment such as mobile phones and notebook computers, electric vehicles and large-scale energy storage devices due to the advantages of high energy density, environmental friendliness, long cycle life and the like.
However, as the limiting voltage of the positive electrode material is continuously increased, the gram capacity of the battery material is gradually increased, and meanwhile, the high-temperature performance of the battery is seriously deteriorated, and the long cycle life cannot be ensured. Especially, in the long-term cyclic charge and discharge process under high voltage (more than 4.5V), the volume of the material expands and causes serious cracks, so that the solvent in the electrolyte enters the inside of the positive electrode material to damage the structure of the positive electrode material, and finally the problem of serious capacity attenuation of the lithium battery is caused.
In the related art, a functional additive is generally used to form a stable interfacial protection layer, i.e., a positive electrode electrolyte interfacial film (CEI), between the positive electrode and the electrolyte to improve the cycle life of the positive electrode. However, the CEI rich in organic matters is combined with the surface of the positive electrode, and cannot bear large volume change of the positive electrode, so that breakage occurs in the process of lithium ion deintercalation, and continuous side reaction occurs between the positive electrode and the electrolyte. And the bonding between CEI rich in inorganic matters and the positive electrode is weaker, the strain/stress born in the positive electrode volume change process is smaller, and the protective effect on the positive electrode can be kept.
However, it is very difficult to form an inorganic-rich CEI on the positive electrode, and thus it is necessary to develop a novel functional additive capable of forming a stable protective film on the positive electrode and improving the high-temperature cycle performance of the battery.
Disclosure of Invention
In order to solve or partially solve the problems in the related art, the application provides an electrolyte additive, an electrolyte and a lithium ion battery, which can form a stable protective film on the anode and the cathode and improve the high-temperature cycle performance of the lithium ion battery.
In a first aspect, the present application provides an electrolyte additive comprising a first additive comprising a compound of formula one:
in the structural formula I, R1, R2, R3, R4, R5 and R6 are respectively a halogen substituted or unsubstituted setting group or a null bond, wherein the setting group is one or more of phenyl, biphenyl, alkyl with 1-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, alkylene with 1-20 carbon atoms, phenylalkyl with 6-26 carbon atoms and condensed ring aryl with 6-26 carbon atoms; x is one of N, C, P and S, and n is a natural number.
As an alternative embodiment, when the setting group is an alkane group of 1 to 20 carbon atoms, the alkane group of 1 to 20 carbon atoms includes a chain group including a straight chain group and a branched group, and a cyclic group substituted or unsubstituted; and/or n is an integer from 0 to 3.
As an alternative embodiment, the first additive comprises at least one of the following compounds:
as an alternative embodiment, the electrolyte additive further comprises a second additive comprising a compound of formula two:
in the structural formula II, R7, R8 and R9 are respectively selected from one or more of halogen, alkyl and halogen substituted alkyl.
As an alternative embodiment, the second additive comprises at least one of the following compounds:
as an alternative embodiment, the amounts of the first additive and the second additive satisfy the following conditions:
130≤(Ya+1/5Yb)/(M*N)≤700
wherein Ya is the mass percentage of the first additive, yb is the mass percentage of the second additive, M is the mass of a single-sided anode material layer with unit area on the anode, and the unit is g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the N is the specific surface area of the negative electrode active material, and the unit is m 2 /g。
As an alternative example, 0.05.ltoreq.ya.ltoreq.5, 5.ltoreq.Yb.ltoreq. 15,0.0045.ltoreq.M.ltoreq. 0.028,0.55.ltoreq.N.ltoreq.2.35.
As an alternative embodiment, the electrolyte additive further includes a sulfonate compound and a nitrile compound.
In a second aspect, the application provides an electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the additive is the electrolyte additive.
The third aspect of the application provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte is the electrolyte.
The technical scheme provided by the application can comprise the following beneficial effects:
the first additive in the application can be oxidized in preference to the electrolyte solvent in the first formation stage, and the oxidation product is electropolymerized on the surface of the positive electrode, so that the direct contact between the electrolyte and the positive electrode material is effectively isolated, the oxidation of the positive electrode protection film under high voltage can be prevented, and the stability of the positive electrode protection film such as CEI film is improved; and because the tetramethyl silane group can remove water, the electrolyte solvent can be subjected to reduction reaction preferentially, the reduction of the anode protective film under high voltage can be prevented, and the stability of the anode protective film such as SEI film is improved. The S-containing heterocyclic functional group in the structural formula I of the first additive can be combined with Li+ in the system, and the generated lithium-rich compound is favorable for the transmission of ions in the electrolyte and accelerates the formation of a stable lithium ion battery system; and the N element in the S-containing heterocyclic functional group belongs to an electron-deficient group, namely a Lewis base, and after ring opening, the N element can be combined with a trace amount of HF in the electrolyte, so that the later side reaction can be reduced, the corrosion of HF on the anode can be inhibited, the dissolution of transition metal ions can be reduced, and the damage of the transition metal ions on the anode protective film can be inhibited. Therefore, the electrolyte additive provided by the embodiment of the application can form a stable protective film on the anode and the cathode, and improves the high-temperature cycle performance of the lithium ion battery.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application as claimed.
Detailed Description
Embodiments of the present application will be described in more detail below. It should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
It should be understood that although the terms "first," "second," "third," etc. may be used herein to describe various information, these information should not be limited by these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the related art, a functional additive is generally used to form a stable interfacial protection layer, i.e., a positive electrode electrolyte interfacial film (CEI), between the positive electrode and the electrolyte to improve the cycle life of the positive electrode. However, the CEI rich in organic matters is combined with the surface of the positive electrode, and cannot bear large volume change of the positive electrode, so that breakage occurs in the process of lithium ion deintercalation, and continuous side reaction occurs between the positive electrode and the electrolyte. And the bonding between CEI rich in inorganic matters and the positive electrode is weaker, the strain/stress born in the positive electrode volume change process is smaller, and the protective effect on the positive electrode can be kept.
However, it is very difficult to form an inorganic-rich CEI on the positive electrode, and thus it is necessary to develop a novel functional additive capable of forming a stable protective film on the positive electrode and improving the high-temperature cycle performance of the battery.
In order to solve the problems, the embodiment of the application provides an electrolyte additive which can form a stable protective film on the anode and the cathode and improve the high-temperature cycle performance of a lithium ion battery.
The embodiment of the application provides an electrolyte additive, which comprises a first additive, wherein the first additive comprises a compound with a structural formula I:
in the structural formula I, R1, R2, R3, R4, R5 and R6 are respectively a halogen substituted or unsubstituted setting group or a null bond, wherein the setting group is one or more of phenyl, biphenyl, alkyl with 1-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, alkenyl with 1-20 carbon atoms, phenylalkyl with 6-26 carbon atoms and condensed ring aryl with 6-26 carbon atoms; x is one of N, C, P and S, and n is a natural number.
The first additive in the embodiment of the application can be oxidized in preference to the electrolyte solvent in the first formation stage, and the oxidation product is electropolymerized on the surface of the positive electrode, so that the direct contact between the electrolyte and the positive electrode material is effectively isolated, the oxidation of the positive electrode protective film under high voltage can be prevented, and the stability of the positive electrode protective film such as CEI film is improved; and because the tetramethyl silane group can remove water, the electrolyte solvent can be subjected to reduction reaction preferentially, the reduction of the anode protective film under high voltage can be prevented, and the stability of the anode protective film such as SEI film is improved. The S-containing heterocyclic functional group in the structural formula I of the first additive can be combined with Li+ in the system, and the generated lithium-rich compound is favorable for the transmission of ions in the electrolyte and accelerates the formation of a stable lithium ion battery system; and the N element in the S-containing heterocyclic functional group belongs to an electron-deficient group, namely a Lewis base, and after ring opening, the N element can be combined with a trace amount of HF in the electrolyte, so that the later side reaction can be reduced, the corrosion of HF on the anode can be inhibited, the dissolution of transition metal ions can be reduced, and the damage of the transition metal ions on the anode protective film can be inhibited. Therefore, the electrolyte additive provided by the embodiment of the application can form a stable protective film on the anode and the cathode, and improves the high-temperature cycle performance of the lithium ion battery.
As an alternative example, when the set group is an alkane group of 1 to 20 carbon atoms, the alkane group of 1 to 20 carbon atoms includes a chain group including a straight chain group and a branched chain group, and a cyclic group, which is substituted or unsubstituted.
Taking an alkane group with 1-20 carbon atoms as an example, the set group may be: ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopentyl, dimethylbutyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, isohexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 1, 2-trimethylpropyl, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, isoheptyl, cycloheptyl, n-octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
As an alternative embodiment, n is an integer from 0 to 3.
In the embodiment of the application, n can be 0, 1,2 and 3.
As an alternative embodiment, the first additive comprises at least one of the following compounds:
as an alternative embodiment, the electrolyte additive further comprises a second additive comprising a compound of formula two:
in the structural formula II, R7, R8 and R9 are respectively selected from one or more of halogen, alkyl and halogen substituted alkyl.
The second additive of the embodiment of the application is a 6-membered cyclic carbonate compound, and compared with the traditional 5-membered ring, the 6-membered cyclic carbonate compound is more stable, is not easy to decompose, and is more suitable for forming a protective film in a higher voltage system. And the carbonate compound has better SEI film forming performance, not only can form a compact structure layer, but also does not increase impedance, can effectively prevent electrolyte from further decomposition, and improves the low-temperature performance of the electrolyte.
As an alternative embodiment, in the structural formula II, R7, R8 and R9 are respectively selected from one or more of halogen, alkyl with 1-12 carbon atoms and halogen substituted alkyl with 1-12 carbon atoms.
As an alternative embodiment, in the structural formula II, R7, R8 and R9 are respectively selected from one or more of halogen, alkyl with 1-6 carbon atoms and halogen substituted alkyl with 1-6 carbon atoms.
As an alternative embodiment, in the structural formula II, R7, R8 and R9 are respectively selected from one or more of fluorine, alkyl of 1-3 carbon atoms and fluorine substituted alkyl of 1-3 carbon atoms.
The second additive provided by the embodiment of the application is fluoro-6-membered cyclic carbonate, can be synergistic with the first additive to be reduced in the anode, and is mainly a LiF and-CHF-OCO 2-type compound, and the products can form a more stable SEI film on the anode to prevent electrolyte from further reductive decomposition on the anode surface.
As a preferred embodiment, the second additive comprises at least one of the following compounds:
as a preferred embodiment, the amounts of the first additive and the second additive satisfy the following conditions:
130≤(Ya+1/5Yb)/(M*N)≤700
wherein Ya is the mass percentage of the first additive, yb is the mass percentage of the second additive, M is the mass of the negative electrode active material per unit area on the single-sided negative electrode, and the unit is g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the N is the specific surface area of the negative electrode active material, and the unit is m 2 /g。
Since the first additive and the second additive mainly form an SEI film at the anode, the amounts of the first additive and the second additive mainly relate to the coating amount of the anode active material. According to the embodiment of the application, the dosage of the first additive and the second additive is controlled by adjusting the ratio of the first additive to the second additive to the coating amount of the anode active material according to the coating amount of the anode active material, and the dosage range meeting the preset requirement on the anode protection effect and the cathode protection effect is obtained according to the test on the battery performance.
As a preferred example, 0.05.ltoreq.ya.ltoreq.5, 5.ltoreq.Yb.ltoreq. 15,0.0045.ltoreq.M.ltoreq. 0.028,0.55.ltoreq.N.ltoreq.2.35.
As a preferred embodiment, the electrolyte additive further includes a sulfonate compound and a nitrile compound.
The sulfonate compound in the embodiment of the present application may be at least one of 1, 3-propane sultone, 1, 3-propene sultone, 1, 4-butane sultone. The nitrile compound may be at least one of succinonitrile, adiponitrile, glutaronitrile, 3' -oxydipropylenenitrile, ethyleneglycol bis (propionitrile) ether, 1,2,3 tris (2-cyanooxy) propane, 1,3, 5-valeronitrile, 1,2, 3-propionitrile and 1,3, 6-hexanetrinitrile.
After the sulfonate compound is added into the electrolyte, a solid electrolyte phase interface film can be formed on the surface of a battery electrode, so that co-intercalation and reductive decomposition of solvent molecules on a negative electrode are inhibited, and the cycle performance and the high-temperature performance of the lithium ion battery are improved.
The cyano functional group contained in the nitrile compound provided by the embodiment of the application can have a stronger complexing effect with transition metal on the surface of the positive electrode material, can form a stable CEI film to protect the positive electrode material, and can inhibit the dissolution of transition metal elements.
In the first formation stage of the electrolyte additive, the electrolyte additive can be oxidized in preference to the electrolyte solvent, and the oxidation product is subjected to electropolymerization on the surface of the positive electrode, so that the direct contact between the electrolyte and the positive electrode material is effectively isolated, the oxidation of the positive electrode protective film under high voltage can be prevented, and the stability of the positive electrode protective film such as CEI film is improved; and because the tetramethyl silane group can remove water, the electrolyte solvent can be subjected to reduction reaction preferentially, the reduction of the anode protective film under high voltage can be prevented, and the stability of the anode protective film such as SEI film is improved. The S-containing heterocyclic functional group in the structural formula I of the first additive can be combined with Li+ in the system, and the generated lithium-rich compound is favorable for the transmission of ions in the electrolyte and accelerates the formation of a stable lithium ion battery system; and the N element in the S-containing heterocyclic functional group belongs to an electron-deficient group, namely a Lewis base, and after ring opening, the N element can be combined with a trace amount of HF in the electrolyte, so that the later side reaction can be reduced, the corrosion of HF on the anode can be inhibited, the dissolution of transition metal ions can be reduced, and the damage of the transition metal ions on the anode protective film can be inhibited. Therefore, the electrolyte additive provided by the embodiment of the application can form a stable protective film on the anode and the cathode, and improves the high-temperature cycle performance of the lithium ion battery.
In addition to the first additive, the second additive is introduced, and the introduced second additive is fluorinated 6-membered cyclic carbonate, so that compared with the traditional 5-membered cyclic carbonate, the 6-membered cyclic carbonate is more stable and is not easy to decompose, and is more suitable for forming a protective film in a higher voltage system, and the second additive can be synergistic with the first additive to preferentially reduce at a negative electrode, and main products are LiF and-CHF-OCO 2-type compounds, and the products can form a more stable SEI film at the negative electrode to prevent electrolyte from further reduction decomposition at the surface of the negative electrode.
And the dosages of the first additive and the second additive meet the following conditions: 130-700,0.05-5 Yb, 5-15,0.0045-M-0.028,0.55-N-2.35; wherein Ya is the mass percentage of the first additive, yb is the mass percentage of the second additive, M is the mass of a single-sided anode material layer with unit area on the anode, and the unit is g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the N is the specific surface area of the negative electrode active material, and the unit is m 2 And/g. Under this condition, the protection effect of the two additives on the anode and the cathode is optimal.
Corresponding to the embodiment of the application function implementation method, the application also provides electrolyte, a lithium ion battery and corresponding embodiments.
The embodiment of the application provides an electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive is the electrolyte additive.
In the electrolyte of the embodiment of the application, the content of the first additive is 0.5-10% of the total weight of the electrolyte.
The lithium salt in the electrolyte of the embodiment of the application is at least one selected from organic lithium salts and inorganic lithium salts.
Preferably, the lithium salt is selected from at least one of fluorine-containing compounds and lithium-containing compounds.
Still further, the lithium salt is at least one selected from the group consisting of hexafluorophosphate, hexafluoroarsenate, perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl and lithium difluoroimide sulfonate.
Preferably, the lithium salt concentration is 0.5M to 1.5M. The concentration of lithium salt is too low, and the conductivity of the electrolyte is low, so that the multiplying power and the cycle performance of the whole battery system can be influenced; the too high concentration of lithium salt and the too high viscosity of the electrolyte also affect the multiplying power of the whole battery system.
Further, the lithium salt concentration is 0.8-1.3M.
Preferably, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
As a preferred embodiment, the electrolyte consists of an organic solvent, a lithium salt and an additive.
As a preferred embodiment, the additive consists of a first additive, a second additive, a sulfonate compound, and a nitrile compound.
The embodiment of the application provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte is the electrolyte.
In the lithium ion battery, the positive electrode comprises a positive electrode current collector and a positive electrode active slurry layer positioned on the positive electrode current collector, wherein the positive electrode active slurry layer comprises a positive electrode active material; the negative electrode includes a negative electrode current collector and a negative electrode active slurry layer on the negative electrode current collector, wherein the negative electrode active slurry layer includes a negative electrode active material. The specific types of the positive electrode active material, the positive electrode binder and the negative electrode active material are not particularly limited, and may be selected according to requirements.
Preferably, the positive electrode active material is one or more selected from lithium cobaltate (LiCoO 2), lithium nickel manganese cobalt ternary material, lithium iron phosphate (LiFePO 4), and lithium manganate (LiMn 2O 4).
Preferably, the anode active material is graphite and/or silicon, for example, natural graphite, artificial graphite, mesocarbon microbeads (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO, snO2, spinel-structured lithiated TiO2-Li4Ti5O12, li-Al alloy may be used as the anode active material.
The first additive in the embodiment of the application can be oxidized in preference to the electrolyte solvent in the first formation stage, and the oxidation product is electropolymerized on the surface of the positive electrode, so that the direct contact between the electrolyte and the positive electrode material is effectively isolated, the oxidation of the positive electrode protective film under high voltage can be prevented, and the stability of the positive electrode protective film such as CEI film is improved; and because the tetramethyl silane group can remove water, the electrolyte solvent can be subjected to reduction reaction preferentially, the reduction of the anode protective film under high voltage can be prevented, and the stability of the anode protective film such as SEI film is improved. The S-containing heterocyclic functional group in the structural formula I of the first additive can be combined with Li+ in the system, and the generated lithium-rich compound is favorable for the transmission of ions in the electrolyte and accelerates the formation of a stable lithium ion battery system; and the N element in the S-containing heterocyclic functional group belongs to an electron-deficient group, namely a Lewis base, and after ring opening, the N element can be combined with a trace amount of HF in the electrolyte, so that the later side reaction can be reduced, the corrosion of HF on the anode can be inhibited, the dissolution of transition metal ions can be reduced, and the damage of the transition metal ions on the anode protective film can be inhibited. Therefore, the electrolyte additive provided by the embodiment of the application can form a stable protective film on the anode and the cathode, and improves the high-temperature cycle performance of the lithium ion battery.
Corresponding to the embodiment of the application function implementation method, the application also provides a terminal and a corresponding embodiment.
The terminal comprises a shell, and electronic components and batteries which are accommodated in the shell, wherein the batteries supply power for the electronic components, and the batteries comprise the lithium ion batteries.
For a further understanding of the present application, the present application is illustrated below in conjunction with the following examples, which are provided to illustrate the application and not to limit the scope of the application.
1. Preparation of electrolyte additives
The electrolyte additive comprises a first additive, a second additive, a sulfonate compound, a nitrile compound and a film forming additive, wherein the sulfonate compound, the nitrile compound and the film forming additive are respectively 1, 3-propane sultone, succinonitrile and vinyl sulfate, and the first additive is selected from a compound 1 with the following structural formula:
the second additive is selected from compound 4 with the following structural formula:
the first and second additives of examples 1-9, and comparative examples 1-7 were formulated in the proportions shown in Table 1.
2. Preparation of electrolyte
The preparation steps of the electrolyte are as follows: the EC/PC/DEC/pp=1/1/2/6 mass ratio was mixed as an organic solvent. Adding a sulfonate compound, a nitrile compound and a film forming additive into an organic solvent, uniformly mixing, adding LiPF6 as a lithium salt to obtain a mixed solution with LiPF6 concentration of 1.1mol/L, and adding the first additive and the second additive prepared in the above manner into the mixed solution to prepare the electrolyte of examples 1-9 and comparative examples 1-7.
3. Manufacturing of battery
1. Manufacturing a positive plate:
the positive electrode active material LCO, the conductive agent CNT and the binder polyvinylidene fluoride are fully stirred and mixed in an N-methyl pyrrolidone solvent according to the mass ratio of 97:1.5:1.5, so that uniform positive electrode slurry is formed. And (3) coating the slurry on an anode current collector Al foil, and drying and cold pressing to obtain the anode plate.
2. Manufacturing a negative plate:
and (3) fully stirring and mixing the anode active material graphite, the conductive agent acetylene black, the binder styrene-butadiene rubber and the thickener sodium carboxymethyl cellulose in a proper amount of deionized water solvent according to the mass ratio of 95:2:2:1, so that uniform anode slurry is formed. And coating the slurry on a negative current collector Cu foil, and drying and cold pressing to obtain a negative plate.
3. Manufacturing a lithium ion battery:
and sequentially stacking the positive plate, the isolating film and the negative plate, enabling the isolating film to be positioned between the positive electrode and the negative electrode, playing an isolating role, and then winding the isolating film to the bare cell. And placing the bare cell in an outer packaging bag, respectively injecting the electrolyte into the dried battery, and performing procedures such as vacuum packaging, standing, formation, shaping and the like to complete the preparation of the lithium ion battery.
4. Experimental test
1. High temperature cycle testing of batteries
The testing method comprises the following steps: and after the battery is placed at 45+/-2 ℃ for 2 hours, the battery is cycled according to standard charge and discharge, the cycle rate is 1C, and the charge voltage is 3.0-4.5V, and the capacity retention rate of the battery after cycling is calculated. The calculation formula is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity)/(first cycle discharge capacity) ×100%.
2. High temperature storage test of battery:
the testing method comprises the following steps: and (3) charging the battery core with the separated capacity to 4.5V at normal temperature with a current of 0.5C, placing the full-charge battery in an environment of 85 ℃ for 12 hours, thermally measuring the thickness expansion rate, discharging to 3.0V with a current of 0.5C after the battery core is recovered to room temperature, and recording the discharge capacity.
3. 130 ℃ thermal shock test of battery
The testing method comprises the following steps: the battery is placed in an environment of 25+/-2 ℃ according to the standard charge-discharge cycle, the cycle rate is 1C, the charge voltage is 3.0-4.5V, the battery is placed in a 130 ℃ oven after full power, the oven is heated to 130 ℃ at 5+/-2 ℃/min, and the battery is stopped after being kept for 1 h. Whether a fire explosion occurred or not is recorded, YES represents NO fire explosion, and NO represents fire explosion.
TABLE 1 electrolyte additive formulation and test results
As is clear from the above experimental data, the addition amount Ya of the first additive was 3%, the addition amount Yb of the second additive was 5%, and the mass M of the single-sided anode material layer per unit area on the anode was 0.0013g/cm 2 The specific surface area N of the negative electrode active material was 1.8m 2 At/g, the 45℃high temperature cycle and high temperature storage performance of the cell are optimal. And when any condition of 130 < ya+1/5 Yb)/(M x N) is not satisfied, the battery performance is not improved, and even the test requirement is not satisfied. And when any one of conditions of 0.05.ltoreq.ya.ltoreq.5, 5.ltoreq.Yb.ltoreq.15, 0.0045.ltoreq.M.ltoreq.0.028, 0.55.ltoreq.N.ltoreq.2.35 is not satisfied, the effect of protecting the anode and the cathode is not optimal.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing description of embodiments of the application has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. An electrolyte additive comprising a first additive comprising a compound of formula one:
in the structural formula I, R1, R2, R3, R4, R5 and R6 are respectively a halogen substituted or unsubstituted setting group or a null bond, wherein the setting group is one or more of phenyl, biphenyl, alkyl with 1-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, alkylene with 1-20 carbon atoms, phenylalkyl with 6-26 carbon atoms and condensed ring aryl with 6-26 carbon atoms; x is one of N, C, P and S, and n is a natural number.
2. The electrolyte additive according to claim 1, wherein when the set group is an alkane group of 1 to 20 carbon atoms, the alkane group of 1 to 20 carbon atoms includes a chain group including a straight chain group and a branched chain group, and a cyclic group, which is substituted or unsubstituted; and/or n is an integer from 0 to 3.
3. The electrolyte additive of claim 1 wherein the first additive comprises at least one of the following compounds:
4. the electrolyte additive of claim 1 further comprising a second additive comprising a compound of structural formula two:
in the structural formula II, R7, R8 and R9 are respectively selected from one or more of halogen, alkyl and halogen substituted alkyl.
5. The electrolyte additive of claim 4, wherein the second additive comprises at least one of the following compounds:
6. the electrolyte additive of claim 4, wherein the amounts of the first additive and the second additive satisfy the following condition:
130≤(Ya+1/5Yb)/(M*N)≤700
wherein Ya is the mass percentage of the first additive, yb is the mass percentage of the second additive, M is the mass of a single-sided anode material layer with unit area on the anode, and the unit is g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the N is the specific surface area of the negative electrode active material, and the unit is m 2 /g。
7. The electrolyte additive according to claim 6, wherein 0.05.ltoreq.ya.ltoreq.5, 5.ltoreq.Yb.ltoreq. 15,0.0045.ltoreq.M.ltoreq. 0.028,0.55.ltoreq.N.ltoreq.2.35.
8. The electrolyte additive of claim 4, further comprising a sulfonate compound and a nitrile compound.
9. An electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the additive is the electrolyte additive according to any one of claims 1 to 8.
10. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte is the electrolyte of claim 9.
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