CN114846668A - Electrolyte, electrochemical device containing electrolyte and electronic device - Google Patents
Electrolyte, electrochemical device containing electrolyte and electronic device Download PDFInfo
- Publication number
- CN114846668A CN114846668A CN202180007386.7A CN202180007386A CN114846668A CN 114846668 A CN114846668 A CN 114846668A CN 202180007386 A CN202180007386 A CN 202180007386A CN 114846668 A CN114846668 A CN 114846668A
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- CN
- China
- Prior art keywords
- electrolyte
- formula
- lithium
- substituted
- unsubstituted
- Prior art date
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- Granted
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- 239000003792 electrolyte Substances 0.000 title claims description 83
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 91
- -1 lithium salt compound Chemical class 0.000 claims description 46
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 229920005554 polynitrile Polymers 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000004450 alkenylene group Chemical group 0.000 claims description 6
- 125000004419 alkynylene group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 3
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 claims description 3
- JJJUZXKATBRCLI-UHFFFAOYSA-N 2-difluorophosphanyloxyethoxy(difluoro)phosphane Chemical compound FP(F)OCCOP(F)F JJJUZXKATBRCLI-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 claims description 3
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 44
- 229910001416 lithium ion Inorganic materials 0.000 description 44
- 238000003860 storage Methods 0.000 description 34
- 239000010410 layer Substances 0.000 description 33
- 239000002904 solvent Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000007667 floating Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BJEWLOAZFAGNPE-UHFFFAOYSA-N 1-ethenylsulfonylethane Chemical compound CCS(=O)(=O)C=C BJEWLOAZFAGNPE-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- VTWYQAQIXXAXOR-UHFFFAOYSA-N 2-methylsulfonylpropane Chemical compound CC(C)S(C)(=O)=O VTWYQAQIXXAXOR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- UMNZUEWMIREWRV-UHFFFAOYSA-N 2-propan-2-ylsulfonylbutane Chemical compound CCC(C)S(=O)(=O)C(C)C UMNZUEWMIREWRV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012097 LiSbF Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical class [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 1
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KGPPDNUWZNWPSI-UHFFFAOYSA-N flurotyl Chemical compound FC(F)(F)COCC(F)(F)F KGPPDNUWZNWPSI-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 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
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- SRFGYPCGVWVBTC-UHFFFAOYSA-N lithium;dihydrogen borate;oxalic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C(O)=O SRFGYPCGVWVBTC-UHFFFAOYSA-N 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005614 potassium polyacrylate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011734 sodium Substances 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
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
An electrolyte solution, and an electrochemical device and an electronic device including the same, wherein the electrolyte solution includes cyano compounds represented by formula (I) and formula (II).
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to electrolyte, an electrochemical device comprising the electrolyte and an electronic device comprising the electrolyte.
Background
The lithium ion battery has the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, good safety and the like, and is widely applied to electronic products such as cameras, mobile phones, unmanned aerial vehicles, notebook computers, smart watches and the like as a power source.
With the continuous expansion of the application range of lithium ion batteries, the market puts higher demands on the lithium ion batteries, for example, the lithium ion batteries are required to have longer service life and better cycle performance while having high energy density. However, when the energy density of the lithium ion battery is improved, the decomposition of the electrolyte is often accelerated, so that the service life and the cycle performance of the lithium ion battery are affected. Therefore, in view of the above, the development of a suitable electrolyte solution is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
An object of the present application is to provide an electrolyte and an electrochemical device and an electronic device including the same to improve high-temperature storage performance and cycle performance of the electrochemical device.
In a first aspect, the present application provides an electrolyte comprising cyano compounds represented by formula (i) and formula (ii):
wherein the content of the first and second substances,
A 1 independently selected from formula (I-A) or formula (II-A),
m or n are each independently selected from 0 or 1;
R 1 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 each independently selected from the group consisting of a covalent single bond, a substituted or unsubstituted C 1 To C 10 Alkylene or heterocyclylene of (A), substituted or unsubstituted C 2 To C 10 Alkenylene or alkynylene of (a), substituted or unsubstituted C 3 To C 10 With an alkenylene or alicyclic hydrocarbon group, substituted or unsubstituted C 6 To C 10 OfAryl, the substituents of each group being independently selected from fluorine, chlorine, bromine or iodine.
In certain embodiments of the first aspect of the present application, the compound represented by formula (i) comprises at least one of the following compounds:
the compound represented by the formula (II) includes at least one of the following compounds:
in certain embodiments of the first aspect of the present application, the compound of formula (i) is present in an amount W by weight based on the total weight of the electrolyte 1 The mass percentage of the compound represented by the formula (II) is W 2 And satisfies the following conditions: w is more than or equal to 0.01 percent 1 ≤5％，0.001％≤W 2 ≤5％，0.1％≤W 1 +W 2 ≤5％。
In certain embodiments of the first aspect of the present application, the electrolyte solution further comprises a polynitrile-based compound comprising at least one of:
in certain embodiments of the first aspect of the present application, the compound represented by formula (i) is contained by mass% based on the total mass of the electrolyteAn amount of W 1 The mass percentage of the compound represented by the formula (II) is W 2 The mass percentage of the polynitrile compound is W 3 And satisfies the following conditions: w is more than or equal to 0.5 percent 3 ≤7％，0.01≤(W 1 +W 2 )/W 3 ≤1。
In some embodiments of the first aspect of the present application, the electrolyte further comprises a boron-based lithium salt compound including lithium tetrafluoroborate (LiBF) 4 ) At least one of lithium bis (oxalato) borate (LiBOB) or lithium difluoro (oxalato) borate (lidob).
In some embodiments of the first aspect of the present application, the boron-based lithium salt compound is present in an amount W of a percentage by mass based on the total mass of the electrolyte 4 Is 0.1% to 1%.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a P-O bond-based compound comprising at least one of lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, lithium tetrafluorooxalato phosphate, 1, 2-bis ((difluorophosphino) oxy) ethane, trimethyl phosphate, triphenyl phosphate, triisopropyl phosphate, 3,3, 3-trifluoroethyl phosphite, tris (trimethylsilane) phosphate, 2- (2,2, 2-trifluoroethoxy) -1,3, 2-dioxaphosphane 2-oxide.
In some embodiments of the first aspect of the present application, the P — O bond-based compound is present in an amount W based on the total mass of the electrolyte 5 Is 0.1% to 1%.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a sulfur oxygen double bond-based compound including at least one of the compounds represented by formula (iv):
wherein A is 4 At least one selected from the group consisting of formula (IV-A), formula (IV-B), formula (IV-C), formula (IV-D), formula (IV-E):
R 41 and R 42 Each independently selected from the group consisting of a covalent bond, a substituted or unsubstituted C 1 To C 5 Alkyl or alkylene group of (A), substituted or unsubstituted C 1 To C 6 A heterocyclic group of (A), substituted or unsubstituted C 2 To C 10 Alkenyl or alkynyl, substituted or unsubstituted C 3 To C 10 And R is an alicyclic group of 41 And R 42 Can be connected into a ring;
R 43 selected from covalent bond, substituted or unsubstituted C 1 To C 3 Alkylene of (a), substituted or unsubstituted C 2 To C 3 Alkenylene or alkynylene of (a);
wherein the substituent is selected from halogen and substituted or unsubstituted C 1 To C 3 Alkyl, substituted or unsubstituted C 2 To C 3 Alkenyl of, substituted or unsubstituted C 2 To C 3 Alkynyl of (1);
wherein the heteroatom is selected from at least one of N, O or S;
the mass percentage content W of the compound represented by the formula (IV) based on the total mass of the electrolyte 6 Is 0.1 to 8 percent.
In certain embodiments of the first aspect of the present application, the compound represented by formula (iv) comprises at least one of the following compounds:
in some embodiments of the first aspect of the present application, the electrolyte further comprises a cyclic carbonate-based compound including at least one of:
based on the total mass of the electrolyte, the mass percentage content W of the cyclic carbonate compound 7 From 0.1% to 10%;
the electrolyte contains a lithium salt including lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluorobutylsulfonate, lithium perchlorate, lithium aluminate, lithium tetrachloroaluminate, lithium bis (sulfonylimide) (LiN (C) x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) Wherein x is a natural number of 0 to 10, y is a natural number of 0 to 10), lithium chloride, lithium fluoride, based on the total mass of the electrolyte, the mass percentage of the lithium salt W 8 Is 10 to 20 percent.
In a second aspect, an electrochemical device is provided comprising an electrolyte as provided in the first aspect of the present application.
In a third aspect, an electronic device is provided that includes an electrochemical device provided in the second aspect of the present application.
An electrolyte solution including cyano compounds represented by formulas (I) and (II), and an electrochemical device and an electronic device including the same are provided. The cyano compounds represented by the formula (I) and the formula (II) are added into the electrolyte, so that the transition metal in the high valence state of the anode can be stabilized, and meanwhile, oxygen released by the anode can be absorbed, and the continuous decomposition of the electrolyte is inhibited; and interface protective films can be formed on the positive electrode and the negative electrode to protect the surfaces of the positive electrode and the negative electrode, so that the high-temperature storage performance and the cycle performance of the electrochemical device are obviously improved. The electronic device comprising the electrochemical device also has good high-temperature storage performance and cycle performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail by referring to the following embodiments. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments in the present application are within the scope of protection of the present application.
In the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery. It is to be understood by one skilled in the art that the following description is illustrative only and is not intended to limit the scope of the present application.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
In a first aspect, the present application provides an electrolyte comprising cyano compounds represented by formula (i) and formula (ii):
wherein the content of the first and second substances,
A 1 independently selected from formula (I-A) or formula (II-A),
m or n are each independently selected from 0 or 1;
R 1 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 each independently selected from the group consisting of a covalent single bond, a substituted or unsubstituted C 1 To C 10 Alkylene or heterocyclylene of (A), substituted or unsubstituted C 2 To C 10 Alkenylene or alkynylene of (a), substituted or unsubstituted C 3 To C 10 With an alkenylene or alicyclic hydrocarbon group, substituted or unsubstituted C 6 To C 10 And the substituents of each group are independently selected from fluorine, chlorine, bromine or iodine.
The cyano compounds represented by the formulae (I) and (II) of the present application have different steric structures of cyano compound molecules having different numbers of cyano groups, and have different effects on improving electrochemical devices. The cyano compounds represented by the formula (I) and the formula (II) are added into the electrolyte, so that the transition metal in the high valence state of the anode can be stabilized, oxygen released from the anode can be absorbed, the continuous decomposition of the electrolyte is inhibited, and an interface protective film can be formed on the anode and the cathode to protect the surfaces of the anode and the cathode, thereby improving the high-temperature storage performance and the cycle performance of the electrochemical device.
In certain embodiments of the first aspect of the present application, the compound represented by formula (i) comprises at least one of the following compounds:
the compound represented by the formula (II) includes at least one of the following compounds:
in some embodiments of the first aspect of the present application, the electrolyte comprises at least one of the compounds of formula (i-1) to formula (i-9), and the compounds of formula (i) having different structures are allowed to act together to further improve the cycle performance and high-temperature storage performance of the electrochemical device without affecting other properties.
In some embodiments of the first aspect of the present application, the electrolyte solution contains at least one of the compounds of formulae (ii-1) to (ii-16), and the compounds represented by formula (ii) having different structures are allowed to act together to further improve the cycle performance and high-temperature storage performance of the electrochemical device without affecting other properties.
In certain embodiments of the first aspect of the present application, the compound of formula (i) is present in an amount W by weight based on the total weight of the electrolyte 1 The mass percentage of the compound represented by the formula (II) is W 2 And satisfies the following conditions: w is more than or equal to 0.01 percent 1 ≤5％，0.001％≤W 2 ≤5％，0.1％≤W 1 +W 2 Less than or equal to 5 percent. For example, W 1 A value of (d) can be 0.01%, 0.05%, 0.1%, 0.5%, 1.5%, 3%, 5%, or any number between any two of the above numerical ranges; w 2 A value of (d) can be 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1.5%, 3%, 5%, or any number between any two of the above numerical ranges; wherein W 1 +W 2 W is required to be less than or equal to 0.1% 1 +W 2 ≤5％，W 1 +W 2 A value of (b) may be 0.1%, 0.15%, 0.2%, 0.5%, 1%, 2.1%, 2.5%, 3.5%, 4%, 4.5%, 5%, or any number between any two of the above numerical ranges. Wherein the cyano compound represented by the formula (I) is contained in an amount W in percentage by mass 1 And the mass percentage content W of the compound represented by the formula (II) 2 If the value of (c) is too low, the continuous decomposition of the electrolyte cannot be suppressed; if the amount is too high, the cyano compound is easily concentrated on the surfaces of the positive and negative electrodes, and a large steric impedance is formed, which affects the transport of lithium ions and thus the electrochemical performance of the electrochemical device.
This application is achieved by combining W 1 +W 2 The control within the range is beneficial to the cyano compounds represented by the formula (I) and the formula (II) to exert a synergistic effect, can stabilize the transition metal in a high valence state of the anode, absorb oxygen released by the anode, inhibit the decomposition of an electrolyte, form an interface protective film on the anode and the cathode, and protect the surfaces of the anode and the cathode, thereby effectively improving the high-temperature performance of an electrochemical deviceStorage performance and cycling performance.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a polynitrile compound comprising at least one of:
by selecting the polynitrile compound, the cycle performance and the high-temperature storage performance of the electrochemical device can be further improved.
In certain embodiments of the first aspect of the present application, the compound represented by formula (i) is present in an amount W by mass based on the total mass of the electrolyte 1 The mass percentage of the compound represented by the formula (II) is W 2 The mass percentage of the polynitrile compound is W 3 And satisfies the following conditions: w is more than or equal to 0.5 percent 3 ≤7％，0.01≤(W 1 +W 2 )/W 3 Less than or equal to 1. The mass percentage content W of the polynitrile compound 3 A value of (b) may be 0.5%, 1%, 1.5%, 2%, 3%, 4%, 4.5%, 5%, 5.5%, 6, 6.5%, 7%, or any number between any two of the above numerical ranges. The inventors of the present application found that (W) 1 +W 2 )/W 3 Too high, for example above 1%, leads to too large a sum of the contents of formula (I) and formula (II) or to too small a content of polynitrile compounds. If the sum of the contents of the formulae (I) and (II) is too high, not only the viscosity of the electrolyte increases, but also an interfacial film having a large resistance is formed on the surfaces of the positive and negative electrodes. The polynitrile compound content is too low to protect the positive electrode well. These effects can affect the electrochemical performance of the electrochemical device. By controlling (W) 1 +W 2 )/W 3 The value of (b) is within the above range, the cycle performance and high-temperature storage performance of the electrochemical device can be improved.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a boron-based lithium salt compound including lithium tetrafluoroborate (LiBF) 4 ) Two, twoAt least one of lithium oxalate borate (LiBOB) or lithium difluoro oxalate borate (lidob). In an electrochemical device, with the increase of the lithium removal amount, oxygen radicals on the surface of the positive electrode are relatively more active, and boron atoms can form stable covalent bonds with the oxygen radicals, so that the loss of the oxygen radicals is effectively inhibited. In addition, by adding the boron lithium salt compound to the electrolyte, a stable Solid Electrolyte Interface (SEI) film can be formed on the negative electrode, and the negative electrode is prevented from being damaged by the transition metal dissolved in the positive electrode. Thus, the addition of the boron-based lithium salt compound in the electrolyte can further improve the cycle performance and high-temperature storage performance of the electrochemical device.
In some embodiments of the first aspect of the present application, the boron-based lithium salt compound is present in an amount W of a percentage by mass based on the total mass of the electrolyte 4 Is 0.1% to 1%. For example, W 4 The value of (b) may be 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, or any value between any two of the above numerical ranges. Mass percentage content W of boron lithium salt compound 4 Too high (e.g., greater than 1%), which is difficult to completely consume during the formation of the electrochemical device, and decomposes during storage of the electrochemical device to generate a large amount of gas, which affects the high-temperature storage performance of the electrochemical device. By mixing W 4 The value of (b) is controlled within the above range, and the cycle performance and high-temperature storage performance of the electrochemical device can be effectively improved.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a P-O bond-type compound including lithium difluorophosphate (LiPO) 2 F 2 ) Lithium difluorobis (oxalato) phosphate (LiDFOP), lithium tetrafluorooxalato phosphate (LiTFOP), 1, 2-bis ((difluorophosphino) oxy) ethane, trimethyl phosphate, triphenyl phosphate, triisopropyl phosphate, 3,3, 3-trifluoroethyl phosphite, tris (trimethylsilane) phosphate, 2- (2,2, 2-trifluoroethoxy) -1,3, 2-dioxaphosphane 2-oxide. By adding the P-O bond compound into the electrolyte, the contact between the electrolyte and the positive electrode and the negative electrode can be reduced, and the effect of inhibiting gas generation is achieved, so that the cycle performance and the high-temperature storage performance of the electrochemical device are effectively improved.
In some embodiments of the first aspect of the present application, the P — O bond-based compound is present in an amount W based on the total mass of the electrolyte 5 Is 0.1% to 1%. By mixing W 5 The value of (b) is controlled within the above range, and the cycle performance and high-temperature storage performance of the electrochemical device can be effectively improved.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a sulfur oxygen double bond-based compound including at least one of the compounds represented by formula (iv):
wherein A is 4 At least one selected from the group consisting of formula (IV-A), formula (IV-B), formula (IV-C), formula (IV-D), formula (IV-E):
R 41 and R 42 Each independently selected from the group consisting of a covalent bond, a substituted or unsubstituted C 1 To C 5 Alkyl or alkylene group of (A), substituted or unsubstituted C 1 To C 6 A heterocyclic group of (A), substituted or unsubstituted C 2 To C 10 Alkenyl or alkynyl, substituted or unsubstituted C 3 To C 10 And R is an alicyclic group of 41 And R 42 Can be connected into a ring;
R 43 selected from covalent bond, substituted or unsubstituted C 1 To C 3 Alkylene of (a), substituted or unsubstituted C 2 To C 3 Alkenylene or alkynylene of (a);
wherein the substituent is selected from halogen and substituted or unsubstituted C 1 To C 3 Alkyl, substituted or unsubstituted C 2 To C 3 Alkenyl of, substituted or unsubstituted C 2 To C 3 Alkynyl of (a);
wherein the heteroatom is selected from at least one of N, O or S;
the mass percentage content W of the compound represented by the formula (IV) based on the total mass of the electrolyte 6 Is 0.1 to 8 percent. For example, W 6 A value of (b) may be 0.1%, 0.3%, 0.5%, 1%, 1.5%, 2%, 3%, 5%, 6%, 7%, 7.5%, 8%, or any value between any two of the above numerical ranges, e.g., may be 1.5% to 6%. The mass percentage content W of the compound represented by the formula (IV) 6 Too high (e.g., greater than 8%), can easily form acidic species, corrode the positive electrolyte interface (CEI) film and the positive electrode material layer, affect the stability of the positive electrode material structure, and further affect the cycle performance of the electrochemical device. By adding W to the sulfur-oxygen double bond compound 6 The control within the above range is more favorable for improving the cycling stability of the electrochemical device, and further improving the cycling performance and the storage performance of the electrochemical device.
In the application, the sulfur-oxygen double bond compound has stronger oxidation resistance, can protect the stability of a positive interface, can be reduced on the surface of a negative electrode to form a layer of protective film, inhibits the decomposition of electrolyte, and further enhances the stability of the interface, thereby further improving the high-temperature storage performance and the cycle performance of the electrochemical device.
In certain embodiments of the first aspect of the present application, the compound represented by formula (iv) comprises at least one of the following compounds:
the electrolyte comprises at least one of compounds shown in formulas (IV-1) to (IV-41), so that the sulfur-oxygen double bond compounds with different structures act together to further improve the cycle performance and the high-temperature storage performance of the electrochemical device without affecting other performances.
In some embodiments of the first aspect of the present application, the electrolyte further comprises a cyclic carbonate-based compound including at least one of:
based on the total mass of the electrolyte, the mass percentage content W of the cyclic carbonate compound 7 Is 0.1% to 10%. For example, W 7 A value of (b) may be 0.1%, 0.5%, 1%, 1.5%, 2%, 3%, 5%, 6%, 7%, 8%, 8.5%, 9%, 10%, or any value between any two of the above numerical ranges, e.g., may be 1% to 6%. By mixing W 7 Controlling within the above range can effectively improve the cycle performance and storage performance of the electrochemical device.
In the application, the cyclic carbonate compound can enhance the stability of SEI film formation, can increase the flexibility of an SEI film by using the cyclic carbonate compound, further increases the protective effect of an active material, and reduces the interface contact probability of the active material and electrolyte, thereby improving the impedance increase generated by byproduct accumulation in the circulation process and improving the circulation performance of an electrochemical device.
In some embodiments of the first aspect of the present application, the electrolyte comprises a lithium salt including lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (sulfonimide) (LiN (C) x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) Wherein x is a natural number of 0 to 10 and y is a natural number of 0 to 10), lithium perchlorate (LiClO) 4 ) Lithium hexafluoroantimonate (LiSbF) 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) At least one of the lithium salts, the mass percentage content W of the lithium salt 8 Is 10 to 20 percent. Preferably, the electrolyte may include LiPF 6 Due to the factIs LiPF 6 Can give high ionic conductivity and improve the cycle performance of the lithium ion battery. Without being bound to any theory, the inventors of the present application have found that, by controlling the mass percentage of the lithium salt within the above range, it is advantageous to improve the conductivity during the cycling of the electrochemical device, thereby improving the cycling performance of the electrochemical device.
In the present application, the electrolyte may further include other non-aqueous solvents, and the other non-aqueous solvents are not particularly limited as long as the purpose of the present application can be achieved, and may include, for example, but not limited to, at least one of carboxylic ester compounds, ether compounds, or other organic solvents. The above carboxylic ester compounds may include, but are not limited to, at least one of methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, gamma-butyrolactone, 2-difluoroethyl acetate, valerolactone, butyrolactone, ethyl 2-fluoroacetate, ethyl 2, 2-difluoroacetate, or ethyl trifluoroacetate. The ether compound may include, but is not limited to, at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, bis (2,2, 2-trifluoroethyl) ether, 1, 3-dioxane, or 1, 4-dioxane. The above-mentioned other organic solvent may include, but is not limited to, at least one of ethyl vinyl sulfone, methyl isopropyl sulfone, isopropyl sec-butyl sulfone, sulfolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl ethyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, bis (2,2, 2-trifluoroethyl) carbonate. The above-mentioned other nonaqueous solvents are contained in a total amount of 5% to 80%, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any range therebetween, based on the total mass of the electrolyte.
In a second aspect, an electrochemical device is provided comprising an electrolyte as provided in the first aspect of the present application. The electrochemical device has good cycle performance and high-temperature storage performance.
The electrochemical device of the present application further includes an electrode assembly, which may include a separator, a positive electrode, and a negative electrode. The separator serves to separate the positive and negative electrodes to prevent internal short circuits of the electrochemical device, which allow free passage of electrolyte ions, completing the electrochemical charge and discharge process. The number of the separator, the positive electrode, and the negative electrode is not particularly limited as long as the object of the present application can be achieved. The present application does not particularly limit the structure of the electrode assembly as long as the object of the present application can be achieved. For example, the structure of the electrode assembly may include a winding structure or a lamination structure.
The positive electrode of the present application is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode includes a positive electrode current collector and a positive electrode material layer. The positive electrode current collector is not particularly limited as long as the object of the present invention can be achieved. For example, the positive electrode current collector may include an aluminum foil, an aluminum alloy foil, a composite current collector, or the like. The positive electrode material layer of the present application contains a positive electrode material. The kind of the positive electrode material in the present application is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode material may include at least one of lithium nickel cobalt manganese oxide (811, 622, 523, 111), lithium nickel cobalt aluminate, lithium iron phosphate, a lithium rich manganese based material, lithium cobalt oxide, lithium manganese iron phosphate, lithium titanate, or the like. In the present application, the cathode material may further include a non-metal element, for example, the non-metal element includes at least one of fluorine, phosphorus, boron, chlorine, silicon, sulfur, and the like, which can further improve the stability of the cathode material. In the present application, the thickness of the positive electrode current collector and the positive electrode material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode collector is 5 μm to 20 μm, preferably 6 μm to 18 μm. The thickness of the single-sided positive electrode material layer is 30 μm to 120 μm. In the present application, the positive electrode material layer may be provided on one surface in the thickness direction of the positive electrode current collector, and may also be provided on both surfaces in the thickness direction of the positive electrode current collector. The "surface" herein may be the entire region of the positive electrode current collector or a partial region of the positive electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the positive electrode sheet may further comprise a conductive layer, the conductive layer being located between the positive current collector and the positive electrode material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The negative electrode of the present application is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode includes a negative electrode current collector and a negative electrode material layer. The present application is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode current collector may include a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a composite current collector, or the like. The anode material layer of the present application contains an anode material. The kind of the negative electrode material is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode material may include natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, SiO x (0<x<2) And metallic lithium. In the present application, the thickness of the anode current collector and the anode material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the negative electrode current collector is 6 μm to 10 μm, and the thickness of the single-sided negative electrode material layer is 30 μm to 130 μm. In the present application, the negative electrode material layer may be provided on one surface in the thickness direction of the negative electrode current collector, and may also be provided on both surfaces in the thickness direction of the negative electrode current collector. The "surface" herein may be the entire region of the negative electrode current collector or a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the negative electrode tab may further comprise a conductive layer, the conductive layer being located between the negative current collector and the negative electrode material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The conductive agent is not particularly limited as long as the object of the present application can be achieved. For example, the conductive agent may include at least one of conductive carbon black (Super P), Carbon Nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, or graphene. For example, the binder may include at least one of polyvinyl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyamideimide, styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), aqueous acrylic resin, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), or the like.
The lithium ion battery of the present application further includes a separator, and the present application does not particularly limit the separator as long as the object of the present application can be achieved. For example, the separator may include a substrate layer and a surface treatment layer. The substrate layer may be a non-woven fabric, a film or a composite film having a porous structure, and the material of the substrate layer may include at least one of Polyethylene (PE), polypropylene (PP), polyethylene terephthalate, polyimide, and the like. Optionally, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film may be used. Optionally, a surface treatment layer is disposed on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance. For example, the inorganic layer includes inorganic particles and a binder, and the inorganic particles are not particularly limited and may be, for example, at least one selected from alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium sulfate, and the like. The binder is not particularly limited, and may be, for example, at least one selected from polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and the like. The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and the like.
The electrochemical device of the present application is not particularly limited, and may include any device in which electrochemical reactions occur. In some embodiments, the electrochemical device may include, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery (lithium ion battery), a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like.
In a third aspect, an electronic device is provided that includes an electrochemical device provided in the second aspect of the present application. The electronic device has good cycle performance and high-temperature storage performance.
The electronic device of the present application is not particularly limited, and may include, but is not limited to, the following categories: notebook computers, pen-input computers, mobile computers, electronic book players, cellular phones, portable facsimile machines, portable copiers, portable printers, headphones, video recorders, liquid crystal televisions, portable cleaners, portable CD players, mini-discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting fixtures, toys, game machines, clocks, electric tools, flashlights, cameras, large household batteries, and the like.
The present application will be specifically described below with reference to examples, but the present application is not limited to these examples.
Test methods and apparatus for examples 1-47, comparative example 1:
and (3) testing the cycle performance:
the lithium ion battery is charged to 4.5V at 0.7C and to 0.05C at 4.5V under a constant voltage condition at 25 ℃. Then, the discharge was carried out to 3.0V at a current of 0.7C, and the cycle was repeated 800 times at a flow of 0.7C charge and 1C discharge. Capacity retention rate (discharge capacity/initial discharge capacity at 800 cycles) × 100%.
And (3) testing the high-temperature storage performance:
charging the lithium ion battery to 4.5V at a constant current of 0.5C at 25 ℃, then charging at a constant voltage until the current is 0.05C, testing the thickness of the lithium ion battery and recording the thickness as the initial thickness, placing the lithium ion battery in an oven at 85 ℃ for 24h, monitoring the thickness at the moment and recording the thickness as the thickness after storage. The lithium ion battery stored at high temperature for 24 hours has a storage thickness expansion rate (%) (after storage thickness-initial thickness)/initial thickness x 100%, and the storage thickness expansion rate exceeding 50% is dangerous, and the test is stopped.
And (3) testing the floating charge performance:
discharging the lithium ion battery to 3.0V at 45 ℃ by 0.5C, then charging to 4.5V by 0.5C, charging to 0.05C at constant voltage under 4.5V, testing the thickness of the lithium ion battery and recording the thickness as the initial thickness, placing the lithium ion battery in a 45 ℃ oven, charging for 30 days at constant voltage of 4.5V, monitoring the thickness change, recording the thickness as the thickness after floating charge, and stopping the test when the floating charge thickness expansion rate (%) of the lithium ion battery is (the thickness after floating charge-the initial thickness)/the initial thickness x 100% and the floating charge thickness expansion rate exceeds 50% and is dangerous.
Example 1
< preparation of electrolyte solution >
In an argon atmosphere glove box with the water content of less than 10ppm, Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethyl Propionate (EP) and Propyl Propionate (PP) are uniformly mixed according to the mass ratio of 1:1:1:1:1 to form a base solvent. Further adding a compound represented by the formula (I) of formula (I), a compound represented by the formula (II) of formula (II) and a well-dried lithium salt LiPF to the above-mentioned base solvent 6 And the lithium salt is dissolved by stirring uniformly. Based on the total mass of the electrolyte, the mass percentage of the formula (I-1) is 0.1 percent, the mass percentage of the formula (II-1) is 0.001 percent, and lithium salt LiPF 6 The mass percentage of the solvent is 12.5 percent, and the balance is the mass percentage of the basic solvent.
< preparation of Positive electrode sheet >
The positive electrode material lithium cobaltate (LiCoO) 2 ) Mixing conductive carbon black serving as a conductive agent, conductive slurry and polyvinylidene fluoride (PVDF) serving as a binder according to the weight ratio of 97.9:0.4:0.5:1.2, adding N-methylpyrrolidone (NMP) serving as a solvent, fully stirring and mixing to prepare anode slurry with the solid content of 75 wt%; the positive electrode is connected with a positive electrodeThe slurry is evenly coated on two surfaces of an aluminum foil of a positive current collector with the thickness of 10 mu m, the aluminum foil is dried at the temperature of 90 ℃, a positive pole piece with the thickness of 100 mu m on a single-side coating is obtained after cold pressing, and the compaction density of the positive pole is 4.15g/cm 3 . And cutting the positive pole piece for later use.
< preparation of negative electrode sheet >
Mixing graphite serving as a negative electrode material, Styrene Butadiene Rubber (SBR) serving as a binder and sodium carboxymethyl cellulose (CMC) serving as a thickening agent according to a weight ratio of 97.4:1.4:1.2, adding deionized water serving as a solvent, and fully stirring and mixing to prepare negative electrode slurry with the solid content of 70 wt%; uniformly coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil with the thickness of 8 mu m, drying at 90 ℃, and cold-pressing to obtain a negative electrode piece with the thickness of 150 mu m on the single-side coating, wherein the compaction density of the negative electrode is 1.80g/cm 3 . And cutting the negative pole piece for later use.
< preparation of separator >
A Polyethylene (PE) porous polymer film having a thickness of 5 μm was used as the separator.
< preparation of lithium ion Battery >
Stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play a role in isolation, and then winding to obtain a bare cell; and (3) placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried cell, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
Example 2 to example 17
The preparation steps of < preparation of electrolyte >, < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > are the same as those of example 1, and the changes of the relevant preparation parameters and performance parameters are shown in table 1.
Examples 18 to 47
< preparation of electrolyte solution >
At least one of a sulfur-oxygen double bond-based compound, a polynitrile-based compound, or a boron-based lithium salt compound is added in addition to the compound represented by formula (I) and the compound represented by formula (II) to the base solvent, and the changes of the relevant production parameters and performance parameters are shown in Table 2, and the rest is the same as example 1.
The preparation steps of < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 1.
Comparative example 1
< preparation of electrolyte solution >
The procedure of example 1 was repeated except that the compound represented by the formula (I) and the compound represented by the formula (II) were not added to the base solvent, and the changes in the preparation parameters and the performance parameters were as shown in Table 1.
The preparation steps of < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 1.
Example 48 to example 66, comparative example 2 test method and apparatus:
and (3) testing the cycle performance:
the lithium ion battery is charged to 4.2V at 1C and to 0.05C at 4.2V under constant voltage at 25 ℃. Then, the current of 1C is discharged to 2.8V, and the process of 1C charging and 4C discharging is carried out circularly for 800 circles. Capacity retention rate (discharge capacity/initial discharge capacity at 800 cycles) × 100%.
And (3) testing the high-temperature storage performance:
charging the lithium ion battery to 4.2V at a constant current of 0.5C at 25 ℃, then charging at a constant voltage until the current is 0.05C, testing the thickness of the lithium ion battery and recording as the initial thickness; the plate was placed in an oven at 85 ℃ for 6h, and the thickness at this time was monitored and recorded as the post-storage thickness. The lithium ion battery is stored for 6h at high temperature, the storage thickness expansion rate (%) is (thickness after storage-initial thickness)/initial thickness x 100%, the storage thickness expansion rate is more than 50%, and the test is stopped.
Example 48
< preparation of electrolyte solution >
At a water content of less than 1In a 0ppm argon atmosphere glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC) and diethyl carbonate (DEC) are uniformly mixed according to the mass ratio of 3:3:4 to form a basic solvent. Further adding a compound represented by the formula (I) of formula (I), a compound represented by the formula (II) of formula (II) and a well-dried lithium salt LiPF to the above-mentioned base solvent 6 And the lithium salt is dissolved by stirring uniformly. Based on the total mass of the electrolyte, the mass percentage of the formula (I-1) is 0.5 percent, the mass percentage of the formula (II-1) is 0.5 percent, and lithium salt LiPF 6 The mass percentage of the solvent is 12.5 percent, and the balance is the mass percentage of the basic solvent.
< preparation of Positive electrode sheet >
Preparing positive electrode material nickel cobalt lithium manganate NCM811 (molecular formula LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) Mixing acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to a weight ratio of 96:2:2, adding N-methylpyrrolidone (NMP) serving as a solvent, fully stirring and mixing to prepare anode slurry with the solid content of 75 wt%; coating the positive electrode slurry on two surfaces of a positive electrode current collector aluminum foil with the thickness of 10 mu m, drying at 90 ℃, and cold-pressing to obtain a positive electrode piece with the thickness of 100 mu m on the single-side coating, wherein the positive electrode compaction density is 3.50g/cm 3 . And cutting the positive pole piece for later use.
The preparation steps of < preparation of negative electrode plate >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 1.
Example 49 to example 51
The preparation steps of < preparation of electrolyte >, < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 48, and the changes of the relevant preparation parameters and performance parameters are shown in table 3.
Example 52 to example 66
< preparation of electrolyte solution >
At least one of a sulfur-oxygen double bond-based compound, a P-O bond-based compound or a cyclic carbonate-based compound was added in addition to the compound represented by the formula (I) and the compound represented by the formula (II) to the base electrolyte, and the changes of the relevant production parameters and performance parameters were as shown in Table 3, and the same as in example 48 was repeated.
The preparation steps of < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 48.
Comparative example 2
< preparation of electrolyte solution >
The same procedures as in example 48 were repeated except that the compound represented by the formula (I) and the compound represented by the formula (II) were not added to the base electrolyte, and the changes in the preparation parameters and the performance parameters were as shown in Table 3.
The preparation steps of < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 48.
As can be seen from examples 1 to 17, 48, comparative examples 1 and 2, the addition of the cyano compounds represented by the formulas (I) and (II) to the electrolyte can significantly improve the cycle performance, the float charge performance and the high-temperature storage performance of the lithium ion battery.
As can be seen from examples 1 to 8, the compounds of the formulae (I) and (II) are present in percentages by weight W 1 +W 2 The capacity retention rate of the lithium ion battery tends to increase first and then decrease, and W is added into the lithium ion battery 1 +W 2 The control is in the range of 0.1% to 5%, so that the lithium ion battery has better cycle performance, floating charge performance and high-temperature storage performance.
It can be seen from example 12 and examples 18 to 47 that the cycle performance, the floating charge performance, and the high-temperature storage performance of the lithium ion battery can be further improved by adding at least one of different sulfur-oxygen double bond compounds or polynitrile compounds into the electrolyte of the present application; different kinds of boron lithium salt compounds are added, so that the cycle performance of the lithium ion battery can be improved.
From example 48 to example 50, it can be seen that the addition of lithium salts with different mass percentages to the electrolyte of the present application can improve the cycle performance and high-temperature storage performance of the lithium ion battery. It can be seen from example 48 and examples 51 to 66 that the cycle performance and the high-temperature storage performance of the lithium ion battery can be further improved by adding at least one of different sulfur-oxygen double bond compounds, P — O bond compounds or cyclic carbonate compounds to the electrolyte of the present application.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (14)
1. An electrolyte comprising cyano compounds represented by formula (I) and formula (II):
wherein the content of the first and second substances,
A 1 independently selectFrom formula (I-A) or formula (II-A),
m or n are each independently selected from 0 or 1;
R 1 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 each independently selected from the group consisting of a covalent single bond, a substituted or unsubstituted C 1 To C 10 Alkylene or heterocyclylene of (A), substituted or unsubstituted C 2 To C 10 Alkenylene or alkynylene of (a), substituted or unsubstituted C 3 To C 10 With an alkenylene or alicyclic hydrocarbon group, substituted or unsubstituted C 6 To C 10 And the substituents of each group are independently selected from fluorine, chlorine, bromine or iodine.
2. The electrolyte of claim 1, wherein the compound represented by formula (i) comprises at least one of the following compounds:
the compound represented by the formula (II) includes at least one of the following compounds:
3. the electrolyte as claimed in claim 1, wherein the compound represented by formula (i) is contained in an amount of W by mass based on the total mass of the electrolyte 1 The mass percentage of the compound represented by the formula (II) is W 2 And satisfies the following conditions: w is more than or equal to 0.01 percent 1 ≤5％，0.001％≤W 2 ≤5％，0.1％≤W 1 +W 2 ≤5％。
4. The electrolyte of claim 1, wherein the electrolyte further comprises a polynitrile compound comprising at least one of:
5. the electrolyte as claimed in claim 4, wherein the compound represented by the formula (I) is contained in an amount of W by mass based on the total mass of the electrolyte 1 The mass percentage of the compound represented by the formula (II) is W 2 The mass percentage of the polynitrile compound is W 3 And satisfies the following conditions: w is more than or equal to 0.5 percent 3 ≤7％，0.01≤(W 1 +W 2 )/W 3 ≤1。
6. The electrolyte of claim 1, wherein the electrolyte further comprises a boron-based lithium salt compound including at least one of lithium tetrafluoroborate, lithium dioxalate borate, or lithium difluorooxalate borate.
7. The electrolyte solution according to claim 6, wherein the boron-based lithium salt compound is contained in an amount W by mass percentage based on the total mass of the electrolyte solution 4 Is 0.1% to 1%.
8. The electrolytic solution according to claim 1, wherein the electrolytic solution further contains a P-O bond-type compound including at least one of lithium difluorophosphate, lithium difluorobis (oxalate) phosphate, lithium tetrafluorooxalate phosphate, 1, 2-bis ((difluorophosphino) oxy) ethane, trimethyl phosphate, triphenyl phosphate, triisopropyl phosphate, 3,3, 3-trifluoroethyl phosphite, tris (trimethylsilane) phosphate, 2- (2,2, 2-trifluoroethoxy) -1,3, 2-dioxaphosphane 2-oxide.
9. The electrolyte solution according to claim 8, wherein the P-O bond-based compound is contained in an amount W by mass based on the total mass of the electrolyte solution 5 Is 0.1% to 1%.
10. The electrolytic solution according to claim 1, wherein the electrolytic solution further contains a sulfur oxygen double bond-based compound including at least one of compounds represented by formula (iv):
wherein, A 4 At least one selected from the group consisting of formula (IV-A), formula (IV-B), formula (IV-C), formula (IV-D), formula (IV-E):
R 41 and R 42 Each independently selected from the group consisting of a covalent bond, a substituted or unsubstituted C 1 To C 5 Alkyl or alkylene group of (A), substituted or unsubstituted C 1 To C 6 Heterocyclic radical of (2), substituted or unsubstitutedC of (A) 2 To C 10 Alkenyl or alkynyl, substituted or unsubstituted C 3 To C 10 And R is an alicyclic group of 41 And R 42 Can be connected into a ring;
R 43 selected from covalent bond, substituted or unsubstituted C 1 To C 3 Alkylene of (a), substituted or unsubstituted C 2 To C 3 Alkenylene or alkynylene of (a);
wherein the substituent is selected from halogen and substituted or unsubstituted C 1 To C 3 Alkyl, substituted or unsubstituted C 2 To C 3 Alkenyl of, substituted or unsubstituted C 2 To C 3 Alkynyl of (a);
wherein the heteroatom is selected from at least one of N, O or S;
the mass percentage content W of the compound represented by the formula (IV) based on the total mass of the electrolyte 6 Is 0.1 to 8 percent.
11. The electrolyte of claim 10, wherein the compound represented by formula (iv) comprises at least one of the following compounds:
12. the electrolyte of claim 1, further comprising a cyclic carbonate-based compound including at least one of:
based on the total mass of the electrolyteThe weight percentage content W of the cyclic carbonate compound 7 From 0.1% to 10%;
the electrolyte contains a lithium salt including lithium hexafluorophosphate, lithium bis-sulfonylimide (LiN (C) x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) Wherein x is a natural number of 0 to 10, y is a natural number of 0 to 10), lithium perchlorate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, and the lithium salt is present in a mass percentage W based on the total mass of the electrolyte 8 Is 10 to 20 percent.
13. An electrochemical device comprising the electrolyte of any one of claims 1 to 12.
14. An electronic device comprising the electrochemical device of claim 13.
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| CN105958120A (en) * | 2016-06-28 | 2016-09-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| CN109786824A (en) * | 2019-01-25 | 2019-05-21 | 宁德新能源科技有限公司 | Electrolyte and the electrochemical appliance for using it |
| CN109786835A (en) * | 2019-01-25 | 2019-05-21 | 宁德新能源科技有限公司 | Electrolyte and the electrochemical appliance for using it |
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| KR20210080560A (en) * | 2020-12-23 | 2021-06-30 | 닝더 엠프렉스 테크놀로지 리미티드 | Electrolytes, electrochemical devices and electronics |
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| CN112670578B (en) * | 2020-12-23 | 2022-11-25 | 东莞新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
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| CN105958120A (en) * | 2016-06-28 | 2016-09-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| US20200144672A1 (en) * | 2018-10-30 | 2020-05-07 | Enevate Corporation | Silicon-based energy storage devices with phosphorus containing electrolyte additives |
| CN109786824A (en) * | 2019-01-25 | 2019-05-21 | 宁德新能源科技有限公司 | Electrolyte and the electrochemical appliance for using it |
| CN109786835A (en) * | 2019-01-25 | 2019-05-21 | 宁德新能源科技有限公司 | Electrolyte and the electrochemical appliance for using it |
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| KR20210080560A (en) * | 2020-12-23 | 2021-06-30 | 닝더 엠프렉스 테크놀로지 리미티드 | Electrolytes, electrochemical devices and electronics |
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