CN112909336A - Lithium ion battery electrolyte and lithium ion battery containing same - Google Patents
Lithium ion battery electrolyte and lithium ion battery containing same Download PDFInfo
- Publication number
- CN112909336A CN112909336A CN202110011127.3A CN202110011127A CN112909336A CN 112909336 A CN112909336 A CN 112909336A CN 202110011127 A CN202110011127 A CN 202110011127A CN 112909336 A CN112909336 A CN 112909336A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- ion battery
- lithium ion
- lithium
- unsubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 143
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 89
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 8
- -1 thiophenyl nitrile compounds Chemical class 0.000 claims description 51
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 37
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 35
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- CUPOOAWTRIURFT-UHFFFAOYSA-N thiophene-2-carbonitrile Chemical class N#CC1=CC=CS1 CUPOOAWTRIURFT-UHFFFAOYSA-N 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 29
- 239000010410 layer Substances 0.000 description 18
- 229910013872 LiPF Inorganic materials 0.000 description 17
- 101150058243 Lipf gene Proteins 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- 238000007600 charging Methods 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229920005993 acrylate styrene-butadiene rubber polymer Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material 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
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000005466 carboxylated polyvinylchloride Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 229920005994 diacetyl cellulose Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) 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
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 2
- 229920000131 polyvinylidene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910012715 LiCo1-y Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910014144 LiNi1-y Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- 229910014217 MyO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- SXLDJBWDCDALLM-UHFFFAOYSA-N hexane-1,2,6-tricarbonitrile Chemical compound N#CCCCCC(C#N)CC#N SXLDJBWDCDALLM-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910002096 lithium permanganate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 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
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte, which comprises a non-aqueous organic solvent, a lithium salt and a first additive, wherein the first additive is at least one selected from thiophene nitrile compounds shown in a formula I and a formula II. In addition, the invention also relates to a lithium ion battery containing the electrolyte. Compared with the prior art, when the electrolyte is used for a high-voltage battery system, the electrochemical performance and the safety performance of the battery can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery containing the same.
Background
Compared with other batteries, the lithium ion battery has the advantages of light weight, small volume, high working voltage, high energy density, large output power, high charging efficiency, no memory effect, long cycle life and the like, is widely applied to the field of digital products such as mobile phones, notebook computers and the like, and is considered as one of the best choices of electric vehicles and large energy storage devices. At present, electronic digital products such as smart phones and tablet computers have higher and higher requirements on energy density of batteries, so that commercial lithium ion batteries are difficult to meet the requirements. The adoption of high-capacity anode materials or high-voltage anode materials is the most effective way for improving the energy density of the lithium ion battery.
However, in the high voltage battery, the oxidative decomposition phenomenon of the electrolyte is increased while the charge voltage of the positive electrode material is increased, thereby causing deterioration of the battery performance. In addition, a phenomenon that positive electrode metal ions are eluted during the use of a high-voltage battery is common, and especially after the battery is stored at a high temperature for a long time, the elution of the positive electrode metal ions is further accelerated, so that the retention capacity of the battery is low. The problems of poor high-temperature cycle and high-temperature storage performance of the current commercialized cobalt acid lithium battery with the voltage of more than 4.4V and the ternary-material high-voltage battery generally exist, and the problems are mainly reflected in that the thickness expansion and the internal resistance increase are large after high-temperature cycle, and the capacity is kept low after long-time high-temperature storage. In addition, the electrolyte of the existing lithium ion battery adopts an organic solvent which is volatile and flammable, and accidents such as fire and the like are easy to happen under abuse conditions such as thermal shock and the like of the battery.
In view of the above, it is necessary to provide an electrolyte solution that can achieve both electrochemical performance and safety performance.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the lithium ion battery electrolyte is provided, and when the lithium ion battery electrolyte is used for a high-voltage battery system, the electrochemical performance and the safety performance of the battery can be effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery electrolyte comprises a non-aqueous organic solvent, a lithium salt and a first additive, wherein the first additive is at least one of thiophene nitrile compounds shown in formula I and formula II,
wherein R is1～R6Independently of one another, from hydrogen, halogen, trimethylsilyl, substituted or unsubstituted C1～C10Alkyl, substituted or unsubstituted C2～C10Alkenyl, substituted or unsubstituted C2～C10Alkynyl, substituted or unsubstituted C6～C16Aryl, substituted or unsubstituted C1～C10Alkanesulfonyl, substituted or unsubstituted C1～C10Alkanoyl, substituted or unsubstituted C6～C16An arylsulfonyl group; x1And X2Independently of one another, from substituted or unsubstituted C1～C15Alkylene, substituted or unsubstituted C2～C15Alkenylene, substituted or unsubstituted C2～C15Alkynylene, substituted or unsubstituted C6～C16Arylene, substituted or unsubstituted C5～C15Heteroarylene, phenylene, acetylene, sulfinyl.
As an improvement of the lithium ion battery electrolyte, the thiophenyl nitrile compounds shown in the formulas I and II are selected from at least one of the following compounds:
as an improvement of the lithium ion battery electrolyte, the mass percentage of the first additive is 0.05-2% based on 100% of the total mass of the lithium ion battery electrolyte.
The lithium ion battery electrolyte of the invention is improved by further comprising a second additive, wherein the second additive comprises at least one of fluoroethylene carbonate, vinylene carbonate, 1, 3-propane sultone, vinyl sulfate, methylene methanedisulfonate, propylene sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether and hexanetrinitrile.
In an improvement of the lithium ion battery electrolyte, the mass percentage of the second additive is less than 15% based on 100% of the total mass of the lithium ion battery electrolyte.
As an improvement of the lithium ion battery electrolyte according to the present invention, the lithium salt includes at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
As an improvement of the lithium ion battery electrolyte, the lithium salt accounts for 10-18% of the total mass of the lithium ion battery electrolyte as 100%.
As an improvement of the electrolyte of the lithium ion battery, the non-aqueous organic solvent comprises at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl propionate, propyl propionate, ethyl acetate, ethyl n-butyrate and gamma-butyrolactone.
The second purpose of the invention is: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte, wherein the electrolyte is the lithium ion battery electrolyte in the specification.
As an improvement of the lithium ion battery of the present invention, the positive electrode active material adopted in the positive electrode sheet is lithium cobaltate; the negative electrode active substance adopted in the negative electrode plate is graphite, a silicon-containing composite material or lithium titanate.
Compared with the prior art, the invention has the beneficial effects that:
the lithium ion battery electrolyte at least contains the additive with the structure shown in the formula I or the formula II, the structure shown in the formula I or the formula II is a thienyl nitrile compound, the carbon-nitrogen triple bond in the cyano group has high bond energy and is not easy to be oxidized, and the cyano group has strong coordination capacity and has complexation with metal ions on the surface of the anode and is attached to the surface of the anode, so that the direct contact between the electrolyte and the anode is effectively reduced, the oxidative decomposition of the electrolyte is slowed down, and meanwhile, a more stable and uniform electrode boundary film is formed on the surface of the anode, the corrosion of HF to the anode can be inhibited, and the dissolution of transition metal ions is reduced. In addition, the chemical compounds shown in the formula I and the formula II have high electronegativity and contain double bonds, can be preferentially reduced on the surface of the negative electrode of the battery to form a low-impedance SEI film containing a large amount of dimeric sulfur compounds, and can improve low-temperature characteristics and rate characteristics. Therefore, the electrolyte of the lithium ion battery can effectively improve the cycle performance, the high-temperature storage performance, the safety performance and the low-temperature discharge performance of the high-voltage lithium ion battery.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
1. Lithium ion battery electrolyte
The invention provides a lithium ion battery electrolyte, which comprises a nonaqueous organic solvent, lithium salt and a first additive, wherein the first additive is at least one of thiophenyl nitrile compounds shown in formula I and formula II,
wherein R is1～R6Independently of one another, from hydrogen, halogen, trimethylsilyl, substituted or unsubstituted C1～C10Alkyl, substituted or unsubstituted C2～C10Alkenyl, substituted or unsubstituted C2～C10Alkynyl, substituted or unsubstituted C6～C16Aryl, substituted or unsubstituted C1～C10Alkanesulfonyl, substituted or unsubstituted C1～C10Alkanoyl, substituted or unsubstituted C6～C16An arylsulfonyl group; x1And X2Independently of one another, from substituted or unsubstituted C1～C15Alkylene, substituted or unsubstituted C2～C15Alkenylene, substituted or unsubstituted C2～C15Alkynylene, substituted or unsubstituted C6～C16Arylene, substituted or unsubstituted C5～C15Heteroarylene, phenylene, acetylene, sulfinyl.
In the electrolyte of the lithium ion battery, the thiophenyl nitrile compounds shown in the formula I and the formula II are selected from at least one of the following compounds:
in the lithium ion battery electrolyte, the mass percentage of the first additive is 0.05-2% based on 100% of the total mass of the lithium ion battery electrolyte.
The lithium ion battery electrolyte of the invention also comprises a second additive, wherein the second additive comprises at least one of fluoroethylene carbonate, vinylene carbonate, 1, 3-propane sultone, vinyl sulfate, methylene methanedisulfonate, propylene sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether and hexanetricarbonitrile.
In the lithium ion battery electrolyte, the mass percentage of the second additive is less than 15 percent, based on the total mass of the lithium ion battery electrolyte being 100 percent.
In the lithium ion battery electrolyte, the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
In the lithium ion battery electrolyte, the lithium salt accounts for 10-18% by mass of the total mass of the lithium ion battery electrolyte as 100%.
In the electrolyte of the lithium ion battery, the non-aqueous organic solvent comprises at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl propionate, propyl propionate, ethyl acetate, ethyl n-butyrate and gamma-butyrolactone.
2. Lithium ion battery
The invention provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte, wherein the electrolyte is the lithium ion battery electrolyte.
Positive plate
The positive plate comprises a positive current collector and a positive material layer coated on at least one surface of the positive current collector. The material of the positive electrode current collector includes, but is not limited to, an aluminum foil, and the specific type of the positive electrode material layer is not particularly limited and may be selected as desired.
In the lithium ion battery of the present invention, the positive electrode material layer includes a positive electrode active material including LiCoO2、LiNiO2、LiMnO4、LiCo1-yMyO2、LiNi1-yMyO4And LiNixCoyMnzM1-x-y-zO2Wherein M is at least one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1<1, 0 is less than or equal to z and less than or equal to 1, and x + y + z is less than or equal to 1. Preferably, the positive electrode active material is lithium cobaltate.
In the lithium ion battery of the present invention, the positive electrode material layer may further include a binder that improves the binding of the positive electrode active material particles to each other and also improves the binding of the positive electrode active material to the positive electrode current collector. Non-limiting examples of binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy, nylon, and the like.
In the lithium ion battery of the present invention, the positive electrode material layer may further include a conductive material, thereby imparting conductivity to the electrode. The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
Negative plate
The negative plate comprises a negative current collector and a negative material layer coated on at least one surface of the negative current collector, the negative material layer comprises a negative active material, and the negative active material comprises artificial graphite, natural graphite, hard carbon, soft carbon and SiOxAnd at least one of a silicon-containing composite material and lithium titanate, wherein x is more than or equal to 0 and less than or equal to 2. Preferably, the negative electrode active material is graphite, a silicon-containing composite material, or lithium titanate.
In the lithium ion battery of the present invention, the negative electrode material layer may further include a binder that improves the binding of the negative electrode active material particles to each other and also improves the binding of the negative electrode active material to the negative electrode current collector. Non-limiting examples of binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy, nylon, and the like.
In the lithium ion battery of the present invention, the negative electrode material layer may further include a conductive material, thereby imparting conductivity to the electrode. The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
Diaphragm
In the lithium ion battery of the present invention, the material and shape of the separator used are not particularly limited, and may be any of the techniques disclosed in the prior art.
In the lithium ion battery of the present invention, the separator may include a base material layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be used. At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer comprises inorganic particles and a binder, wherein the inorganic particles are selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is selected from one or a combination of more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
The polymer layer comprises a polymer, and the material of the polymer is selected from at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride and poly (vinylidene fluoride-hexafluoropropylene).
The advantageous effects of the present invention will be described in detail below with reference to examples, comparative examples and performance tests.
The thienylnitriles of the formulae I and II used in the examples are shown in Table 1.
TABLE 1 structural formula of each thienylnitrile compound
Example 1
Preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a1, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 1.
Preparing a soft package battery: stacking the prepared positive plate (active material lithium cobaltate), the diaphragm and the negative plate (active material graphite) in sequence, enabling the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; and (3) placing the bare cell into an aluminum plastic film outer package, injecting the prepared electrolyte into the dried battery, packaging, standing, forming, shaping and grading to finish the preparation of the lithium ion soft package battery.
Example 2
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 2.0 wt% of thienylnitrile compound a1, 5 wt% of fluoroethylene carbonate (FEC) and 0 wt% based on the total weight of the electrolyte5 wt% Vinylene Carbonate (VC) was uniformly stirred to obtain the electrolyte for lithium ion battery of example 2.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 3.0 wt% of thienylnitrile compound a1, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 3.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a2, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 4.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is:
preparing electrolyte: mixing ethylene carbonate, diethyl carbonate and methyl ethyl carbonate in a glove box filled with argon according to the mass ratio of EC: DEC: EMC ═ 1:1:1, and then slowly adding the mixed solution based on the total electrolyte12.5 wt% lithium hexafluorophosphate (LiPF)6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a3, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 5.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a4, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 6.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a5, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 7.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a6, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 8.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a7, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 9.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound A8, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte are added, and after uniform stirring, the mixture is stirredThe lithium ion battery electrolyte of example 10 was obtained.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a9, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 11.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate and propyl propionate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: PP ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a1, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of example 12.
The rest is the same as embodiment 1, and the description is omitted here.
Example 13
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then lithium hexafluorophosphate (LiPF) of 5 wt% based on the total weight of the electrolyte was slowly added to the mixed solution6) And 5 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of thienylnitrile compound a1, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and uniformly stirred to obtain the electrolyte for a lithium ion battery of example 13.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) And uniformly stirring to obtain the lithium ion battery electrolyte of the comparative example 1.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) Finally, 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte is added and uniformly stirred to obtain the lithium ion battery electrolyte of the comparative example 2.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) Finally, 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte are added and stirred uniformlyThen, the lithium ion battery electrolyte of comparative example 3 was obtained.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 4
The difference from example 1 is:
preparing electrolyte: ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate were mixed in a glove box filled with argon gas at a mass ratio of EC: DEC: EMC ═ 1:1:1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 1.25 wt% of lithium bis (fluorosulfonyl) imide (LiTFSI) based on the total weight of the electrolyte, and finally 5 wt% of fluoroethylene carbonate (FEC) and 0.5 wt% of Vinylene Carbonate (VC) based on the total weight of the electrolyte were added and stirred uniformly to obtain the electrolyte for a lithium ion battery of comparative example 4.
The rest is the same as embodiment 1, and the description is omitted here.
The electrolyte compositions of the above examples and comparative examples are detailed in table 2.
TABLE 2 electrolyte compositions of examples and comparative examples
Performance testing
The batteries and the electrolyte thereof prepared in examples 1 to 13 and comparative examples 1 to 4 were subjected to a relevant performance test.
(1) And (3) testing high-temperature cycle performance: at the temperature of 45 ℃, the battery after capacity grading is charged to 4.40V at constant current and constant voltage of 0.7C, the current is cut off at 0.05C, then the battery is discharged to 3.0V at constant current of 0.5C, and the capacity retention rate at the 500 th week is calculated after the battery is charged and discharged for 500 cycles according to the cycle, wherein the calculation formula is as follows:
the 500-week cycle capacity retention ratio (%) (500-week cycle discharge capacity/first-cycle discharge capacity) × 100%.
(2) High temperature storage test at 60 ℃ for 14 d: charging and discharging the battery at room temperature at 0.5C for 1 time (4.40V-3.0V), and recording the discharge capacity C before storage0Then the battery is charged to 4.40V full-voltage by constant current and constant voltage, and the thickness d of the battery before high-temperature storage is tested by using a vernier caliper1(the two diagonals of the battery are respectively connected through a straight line, and the intersection point of the two diagonals is a battery thickness test point), the battery is placed into a 60 ℃ incubator for storage for 14 days, and after the storage is finished, the battery is taken out and the thermal thickness d of the stored battery is tested2Calculating the expansion rate of the thickness of the battery after the battery is stored for 14 days at 60 ℃; after the battery is cooled for 24 hours at room temperature, the battery is discharged to 3.0V at a constant current of 0.5C, then charged to 4.40V at a constant current and a constant voltage of 0.5C, and the discharge capacity C after the battery is stored is recorded1And a charging capacity C2And calculating the capacity residual rate and the recovery rate of the battery after being stored for 14 days at 60 ℃, wherein the calculation formula is as follows:
thickness expansion rate (d) after storage at 60 ℃ for 14 days2-d1)/d1*100％；
Capacity remaining rate after 14 days of storage at 60 ═ C1/C0*100％；
Capacity recovery rate after 14 days of storage at 60 ═ C2/C0*100％。
(3) And (3) testing low-temperature discharge performance: discharging 0.5C of the divided battery to 3.0V at 25 deg.C, and standing for 5 min; charging to 4.40V at 0.2C, changing to 4.40V constant voltage charging when the cell voltage reaches 4.40V, and standing for 5min until the charging current is less than or equal to the given cutoff current of 0.05C; transferring the fully charged core into a high-low temperature box, setting the temperature to be-10 ℃, and standing for 120min after the temperature of the incubator reaches; discharging at 0.2C to stop voltage of 3.0V, and standing for 5 min; then the temperature of the high-low temperature box is adjusted to 25 +/-3 ℃, and the box is placed for 60min after the temperature of the box is reached; charging to 4.40V at 0.2C, and changing to 4.40V constant-voltage charging when the cell voltage reaches 4.40V until the charging current is less than or equal to the given cutoff current of 0.05C; standing for 5 min; the capacity retention rate of 3.0V discharged at the low temperature of-10 ℃ is calculated. The calculation formula is as follows:
capacity retention (%) of 3.0V at 10 ℃ (discharge capacity from-10 ℃ to 3.0V/discharge capacity from 25 ℃ to 3.0V) × 100%.
(4) Thermal shock performance: discharging to 3.0V at a given current of 0.2C under the environment condition of 25 ℃; standing for 5 min; charging to 4.40V at a charging current of 0.2C, and changing to 4.40V constant-voltage charging when the cell voltage reaches 4.40V until the charging current is less than or equal to a given cutoff current of 0.05C; and (3) placing the battery cell into an oven after standing for 1h, raising the temperature of the oven to 135 +/-2 ℃ at the speed of 5 +/-2 ℃/min, keeping for 30min, and stopping, wherein the judgment standard is that the battery cell does not catch fire and does not explode.
The results of the above performance tests are shown in table 3.
TABLE 3 test results
As can be seen from the test results in Table 3, examples 1 to 13 adopting the technical scheme of the invention have good cycle performance, high-temperature storage performance and low-temperature discharge performance; the lithium ion battery adopting the electrolyte of the comparative example 1 has poor output performance and cannot give consideration to both high and low temperature and cycle performance.
Results of comparative examples 1-4 show that the addition of 5% of FEC and 0.5% of VC can obviously improve the cycle performance of the battery cell, but does not improve the storage performance and the safety performance; when 5% of FEC, 0.5% of VC and 1.25% of LiTFSI are added, the additives are synergistically influenced, and the cycle retention rate is further improved.
The results of the comparative example 4 and the examples 1 to 13 show that the examples containing the compound of the structural formula I/II shown in the technical scheme of the invention can improve the cycle, storage performance and safety performance of the battery cell, and the comparison of the examples 1 to 3 shows that the higher the content of the thiophenyl nitrile compound is, the higher the thermal shock pass rate at 135 ℃ for 30min is, and the lower the expansion rate at 60 ℃ in the storage thickness is, so that the low-temperature discharge performance cannot be obviously influenced. In addition, it is shown by the results of examples 1, 12 and 13 that any replacement in the nonaqueous organic solvent and lithium salt exemplified in the present invention does not affect the cell performance.
In summary, the comparison of each example and the comparative example shows that the lithium ion secondary battery containing the electrolyte has good battery output performance by adding the compound shown in the structural formula I or the structural formula II to form a protective film on the positive electrode and the negative electrode in the examples of the invention. The electrolyte is applied to a high-voltage lithium cobaltate system, and has obvious improvement effect.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The electrolyte of the lithium ion battery is characterized by comprising a non-aqueous organic solvent, a lithium salt and a first additive, wherein the first additive is at least one of thiophenyl nitrile compounds shown in a formula I and a formula II,
wherein R is1～R6Independently of one another, from hydrogen, halogen, trimethylsilyl, substituted or unsubstituted C1～C10Alkyl, substituted or unsubstituted C2～C10Alkenyl, substituted or unsubstituted C2～C10Alkynyl, substituted or unsubstituted C6～C16Aryl, substituted or unsubstituted C1～C10Alkanesulfonyl, substituted or unsubstituted C1～C10Alkanoyl, substituted or unsubstituted C6～C16An arylsulfonyl group; x1And X2Independently of one another, from substituted or unsubstituted C1～C15Alkylene, substituted or unsubstituted C2～C15Alkenylene, substituted or unsubstituted C2～C15Alkynylene, substituted or unsubstituted C6～C16Arylene, substituted or unsubstituted C5～C15Heteroarylene, phenylene, acetylene, sulfinyl.
2. The lithium ion battery electrolyte of claim 1 wherein the thienylnitriles of formula i and ii are selected from at least one of the following compounds:
3. the lithium ion battery electrolyte of claim 1 or 2, wherein the mass percentage of the first additive is 0.05-2% based on 100% of the total mass of the lithium ion battery electrolyte.
4. The lithium ion battery electrolyte of claim 1, further comprising a second additive comprising at least one of fluoroethylene carbonate, vinylene carbonate, 1, 3-propane sultone, vinyl sulfate, methylene methanedisulfonate, propylene sultone, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, and hexanetrinitrile.
5. The lithium ion battery electrolyte of claim 4, wherein the second additive is present in an amount of 15% by mass or less based on 100% by mass of the total mass of the lithium ion battery electrolyte.
6. The lithium ion battery electrolyte of claim 1, wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (fluorosulfonato) imide.
7. The lithium ion battery electrolyte of claim 1, wherein the lithium salt is present in an amount of 10 to 18% by mass, based on 100% by mass of the total mass of the lithium ion battery electrolyte.
8. The lithium ion battery electrolyte of claim 1, wherein the non-aqueous organic solvent comprises at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl propionate, propyl propionate, ethyl acetate, ethyl n-butyrate, and γ -butyrolactone.
9. A lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte, and is characterized in that the electrolyte is the lithium ion battery electrolyte of any one of claims 1 to 8.
10. The lithium ion battery according to claim 9, wherein the positive electrode active material used in the positive electrode sheet is lithium cobaltate; the negative electrode active substance adopted in the negative electrode plate is graphite, a silicon-containing composite material or lithium titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110011127.3A CN112909336A (en) | 2021-01-06 | 2021-01-06 | Lithium ion battery electrolyte and lithium ion battery containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110011127.3A CN112909336A (en) | 2021-01-06 | 2021-01-06 | Lithium ion battery electrolyte and lithium ion battery containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112909336A true CN112909336A (en) | 2021-06-04 |
Family
ID=76112207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110011127.3A Pending CN112909336A (en) | 2021-01-06 | 2021-01-06 | Lithium ion battery electrolyte and lithium ion battery containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112909336A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490892A (en) * | 2002-09-16 | 2004-04-21 | H.C.施塔克股份有限公司 | Cyan substituted thiophene electrolyte additive for preventing lithium battery from overcharge |
| CN105226324A (en) * | 2015-10-19 | 2016-01-06 | 东莞市凯欣电池材料有限公司 | A kind of high-voltage electrolyte and use the lithium ion battery of this electrolyte |
| US20180048020A1 (en) * | 2016-08-12 | 2018-02-15 | Lenovo (Beijing) Co., Ltd. | Lithium-ion polymer battery and electronic device |
-
2021
- 2021-01-06 CN CN202110011127.3A patent/CN112909336A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490892A (en) * | 2002-09-16 | 2004-04-21 | H.C.施塔克股份有限公司 | Cyan substituted thiophene electrolyte additive for preventing lithium battery from overcharge |
| CN105226324A (en) * | 2015-10-19 | 2016-01-06 | 东莞市凯欣电池材料有限公司 | A kind of high-voltage electrolyte and use the lithium ion battery of this electrolyte |
| US20180048020A1 (en) * | 2016-08-12 | 2018-02-15 | Lenovo (Beijing) Co., Ltd. | Lithium-ion polymer battery and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11165097B2 (en) | Electrolyte, electrochemical device and electronic device containing the same | |
| CN110931868B (en) | Non-aqueous electrolyte and lithium ion battery containing same | |
| CN110429335B (en) | Electrolyte solution, electrochemical device and electronic device comprising same | |
| JP6015653B2 (en) | Non-aqueous electrolyte and lithium ion battery | |
| WO2016126534A1 (en) | Electrochemical cells that include lewis acid: lewis base complex electrolyte additives | |
| CN109802180B (en) | Electrolyte solution and electrochemical device | |
| CN108242557B (en) | Electrolyte solution and secondary battery | |
| CN110380120B (en) | Electrolyte solution, electrochemical device and electronic device comprising the same | |
| CN111628219A (en) | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device | |
| CN111697266B (en) | Electrolyte solution, and electrochemical device and electronic device including the same | |
| CN113571773B (en) | Lithium ion battery electrolyte and lithium ion battery containing same | |
| CN109830749B (en) | Electrolyte and electrochemical device | |
| CN112768770A (en) | Electrolyte and lithium ion battery containing same | |
| CN112400249A (en) | Electrolyte and electrochemical device | |
| CN111244541A (en) | Electrolyte solution and electrochemical device using the same | |
| JP2016048624A (en) | Lithium secondary battery | |
| CN111900471B (en) | High-voltage electrolyte and lithium ion battery containing same | |
| CN112956063B (en) | Electrolyte and electrochemical device and electronic device including the same | |
| KR20230035681A (en) | Electrochemical and Electronic Devices | |
| CN111697267A (en) | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device | |
| CN112928328A (en) | Lithium ion battery electrolyte containing silane sulfonamide compound and lithium ion secondary battery | |
| CN109119599B (en) | Secondary battery and preparation method thereof | |
| CN110854432B (en) | Electrolyte solution, and electrochemical device and electronic device using same | |
| CN111740162A (en) | Electrolyte solution, electrochemical device including the same, and electronic device | |
| CN111971845A (en) | Electrolyte and electrochemical device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210604 |