CN112687952A - Electrolyte solution, electrochemical device, and electronic device - Google Patents
Electrolyte solution, electrochemical device, and electronic device Download PDFInfo
- Publication number
- CN112687952A CN112687952A CN202011545888.9A CN202011545888A CN112687952A CN 112687952 A CN112687952 A CN 112687952A CN 202011545888 A CN202011545888 A CN 202011545888A CN 112687952 A CN112687952 A CN 112687952A
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- Prior art keywords
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- unsubstituted
- electrolyte
- formula
- lithium
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- 239000008151 electrolyte solution Substances 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 86
- 239000003792 electrolyte Substances 0.000 claims abstract description 86
- 239000000126 substance Substances 0.000 claims abstract description 8
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 43
- 229910003002 lithium salt Inorganic materials 0.000 claims description 34
- 159000000002 lithium salts Chemical class 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 33
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- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical group 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 12
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- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 9
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
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- 125000004429 atom Chemical group 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
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- 239000000654 additive Substances 0.000 description 46
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- 239000007774 positive electrode material Substances 0.000 description 36
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- 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
- LFXDZEWZNBZMRB-UHFFFAOYSA-N 3,3-difluoropropyl acetate Chemical compound CC(=O)OCCC(F)F LFXDZEWZNBZMRB-UHFFFAOYSA-N 0.000 description 1
- LVTJQWGHKKVDST-UHFFFAOYSA-N 3,3-difluoropropyl propanoate Chemical compound CCC(=O)OCCC(F)F LVTJQWGHKKVDST-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910016861 F9SO3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013124 LiNiVO4 Inorganic materials 0.000 description 1
- 229910021466 LiQS2 Inorganic materials 0.000 description 1
- 229910012097 LiSbF Inorganic materials 0.000 description 1
- 229910012946 LiV2O5 Inorganic materials 0.000 description 1
- 229910021462 LiaCoGbO2 Inorganic materials 0.000 description 1
- 229910021464 LiaMn2GbO4 Inorganic materials 0.000 description 1
- 229910021461 LiaNiGbO2 Inorganic materials 0.000 description 1
- 229910021460 LiaNibCocMndGeO2 Inorganic materials 0.000 description 1
- 229910021459 LiaNibEcGdO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910006853 SnOz Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 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
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 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
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 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
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 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
- 239000000571 coke Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- JFKMVZYYHWLTKZ-UHFFFAOYSA-N ethyl 4,4-difluorobutanoate Chemical compound CCOC(=O)CCC(F)F JFKMVZYYHWLTKZ-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
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000011326 fired coke Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910021473 hassium Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000000743 hydrocarbylene group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 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
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VKWKRFYQWSAEFV-UHFFFAOYSA-N methyl 3,3-difluoropropanoate Chemical compound COC(=O)CC(F)F VKWKRFYQWSAEFV-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte, an electrochemical device and an electronic device. The electrolyte includes a compound represented by formula (I); in the formula (I), A1And A2Each independently selected from any one of structural formulas shown in a formula (I-A), a formula (I-B) and a formula (I-C); wherein the content of the first and second substances,
represents a binding site to an adjacent atom; m is selected from 0 or 1; n is an integer of 2 to 6, and, when n is 2 or more, 2 or more R12The same or different. The electrochemical device comprises a positive plate, a negative plate, an isolating membrane and the electrolyte. The electronic device includes the electrochemical device. The use of the compound represented by the formula (I) in the electrolysis can be significantly improved by adding the compound to the electrolyteHigh temperature storage performance and safety performance of liquid electrochemical devices and electronic devices.
Description
Technical Field
The present application relates to an electrolyte, an electrochemical device, and an electronic device.
Background
Electrochemical devices, such as lithium ion batteries, have been receiving much attention due to their characteristics of high energy density, high power density, and stable service life, and thus are widely used. With the rapid development of technology, the diversity of market demands, and the rise of energy storage systems and electric automobile industries in the coming years, more demands are put on lithium ion batteries, such as thinner, lighter, more diversified profiles, higher safety, higher power, higher energy density, and the like.
The above description is merely provided as background and is not an admission that the above "background" constitutes prior art to the present application.
Disclosure of Invention
In some embodiments, the present application provides an electrolyte comprising a compound represented by formula (I);
in the formula (I), the compound represented by the formula (I),
A1and A2Each independently selected from any one of structural formulas shown in a formula (I-A), a formula (I-B) and a formula (I-C);
wherein the content of the first and second substances,
represents a binding site to an adjacent atom;
R11、R12、R14each independently selected from the group consisting of a covalent bond, substituted or unsubstituted C1-C10Alkylene, substituted or unsubstituted C2-C10Alkenylene, substituted or unsubstituted C2-C10Alkynylene, substituted or unsubstituted C3-C10Alkenylene, substituted or unsubstituted C6-C10Arylene, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
R13selected from substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alkenyl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
m is selected from 0 or 1;
n is an integer of 2 to 6, and, when n is 2 or more, 2 or more R12The same or different.
In some embodiments, the compound represented by formula (I) includes at least one of the compounds represented by formula (I-1) to formula (I-16);
in some embodiments, the compound represented by formula (I) is present in an amount of 0.01 to 10% by mass, based on the total mass of the electrolyte.
In some embodiments, the compound represented by formula (I) is present in an amount of 0.01 to 2% by mass, based on the total mass of the electrolyte.
In some embodiments, the electrolyte further includes a sulfur oxygen double bond-containing compound including at least one of compounds represented by formula (II-a) and formula (II-B);
in the formulae (II-A) and (II-B),
R21and R22Each independently selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R21And R22Can be bonded to form a ring structure;
R23and R24Each independently selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R23And R24Can be bonded to form a ring structure.
In some embodiments, the compound containing a thiooxy double bond includes at least one of the compounds represented by formula (II-1) to formula (II-22);
in some embodiments, the sulfur oxygen double bond-containing compound is present in an amount of 0.01 to 10% by mass based on the total mass of the electrolyte.
In some embodiments, the electrolyte further comprises a boron-containing lithium salt comprising at least one of lithium tetrafluoroborate, lithium dioxalate, lithium difluorooxalate borate.
In some embodiments, the boron-containing lithium salt is present in an amount of 0.01 to 3% by mass, based on the total mass of the electrolyte.
In some embodiments, the electrolyte further comprises a lithium salt containing a P-O bond, the lithium salt containing a P-O bond comprising at least one of lithium difluorophosphate, lithium difluorobis-oxalato phosphate, lithium tetrafluorooxalato phosphate.
In some embodiments, the P — O bond-containing lithium salt is present in an amount of 0.01 to 3% by mass, based on the total mass of the electrolyte.
In some embodiments, the present application also provides an electrochemical device comprising a positive electrode tab, a negative electrode tab, a separator, and the above electrolyte.
In some embodiments, the present application also provides an electronic device comprising the electrochemical device described above.
The technical scheme of the application has at least the following beneficial effects: when the compound represented by the formula (I) is added to an electrolytic solution, the high-temperature storage performance and safety performance of an electrochemical device or an electronic device using the electrolytic solution can be remarkably improved.
Detailed Description
It is to be understood that the disclosed embodiments are merely exemplary of the application that may be embodied in various forms and that, therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application.
In the description of the present application, unless explicitly specified or limited otherwise, the terms "first", "second", "third", "fourth", "fifth", "sixth", "formula (I)", "formula (I-A)", "formula (I-B)", "formula (I-C)", "formula (II-A)", "formula (II-B)", "formula (III-A)" etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance and relationship to each other.
In the description of the present application, unless otherwise indicated, the functional groups of all compounds may be substituted or unsubstituted.
In the description of this application, the term "heteroatom" means an atom other than C, H. In some embodiments, the heteroatoms include at least one of B, N, O, Si, P, S, halogen.
In the description of this application, the term "heterocyclyl" refers to a cyclic group that contains at least one heteroatom. In some embodiments, the heterocyclic group comprises at least one of an aliphatic heterocyclic group and an aromatic heterocyclic group.
In the description of the present application, the term "heteroatom-containing functional group" refers to a functional group that includes at least one heteroatom.
In the description of the present application, the term "alkylene" refers to a divalent alkyl group, the term "alkenylene" refers to a divalent alkenyl group, the term "alkynylene" refers to a divalent alkynyl group, and the term "arylene" refers to a divalent aryl group.
In the description of this application, the term "alkenyl" denotes a group in which two alkenyl groups share the same carbon. In some embodiments, the alkenylene group is a divalent alkenylene group having the chemical formula-CH ═ C ═ CH-.
In the description of the present application, the term "alicyclic hydrocarbon group" means a cyclic hydrocarbon having aliphatic properties, and containing a closed carbon ring in the molecule. In some embodiments, the cycloaliphatic hydrocarbylene group is a divalent cycloaliphatic hydrocarbyl group.
(electrolyte)
[ first additive ]
In some embodiments, the electrolyte comprises a first additive comprising a compound represented by formula (I);
in the formula (I), the compound represented by the formula (I),
A1and A2Each independently selected from the group consisting of formula (I-A), formula (I-B), formula (I-C) tableAny one of the structural formulas shown in the specification;
wherein the content of the first and second substances,
represents a binding site to an adjacent atom;
R11、R12、R14each independently selected from the group consisting of a covalent bond, substituted or unsubstituted C1-C10Alkylene, substituted or unsubstituted C2-C10Alkenylene, substituted or unsubstituted C2-C10Alkynylene, substituted or unsubstituted C3-C10Alkenylene, substituted or unsubstituted C6-C10Arylene, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
R13selected from substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alkenyl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
m is selected from 0 or 1;
n is an integer of 2 to 6, and, when n is 2 or more, 2 or more R12The same or different.
The main way to increase the energy density of the electrochemical device may be to increase the charging voltage of the electrochemical device or to increase the capacity of active materials in the electrochemical device. However, these methods tend to accelerate the decomposition of the electrolyte in the electrochemical device. In addition, the trace amount of water in the electrolyte may cause the decomposition of lithium hexafluorophosphate to generate Hydrogen Fluoride (HF), which may further accelerate the decomposition of the electrolyte, resulting in the generation of gas from the electrochemical device.
The addition of the compound represented by formula (I) to the electrolyte can significantly improve the high-temperature storage performance and safety performance of the electrochemical device. This is because, after the compound represented by the formula (I) is added to the electrolyte, the transition metal in a high valence state on the surface of the positive electrode can be stabilized, and hydrogen fluoride in the electrolyte can be absorbed, and the decomposition of the interface film can be slowed down, so that the continuous decomposition of the electrolyte can be suppressed, the gas evolution of the electrochemical device can be reduced, and the high-temperature storage performance and safety performance of the electrochemical device can be significantly improved.
In some embodiments, the compound represented by formula (I) comprises at least one of the compounds represented by formulae (I-1) to (I-16);
in some embodiments, R11、R14Selected from substituted or unsubstituted C1-C10Alkylene, and, when substituted, the substituent is halogen; r12Selected from covalent bond, substituted or unsubstituted C1-C10Alkylene, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen; r13Selected from substituted or unsubstituted C1-C10Alkyl, and, when substituted, the substituent is halogen; m is selected from 1; n is an integer of 2 to 6, and, when n is 2 or more, 2 or more R12The same or different.
In some embodiments, the compound represented by formula (I) is present in an amount of 0.01 to 10% by mass, based on the total mass of the electrolyte. When the mass percentage of the compound represented by formula (I) is within the above range, the high-temperature storage performance and safety performance of the electrochemical device can be further improved; meanwhile, the content of the compound represented by the formula (I) cannot be too high because the compound represented by the formula (I) contains amine functional groups, which are basic functional groups, so that if the content of the compound represented by the formula (I) is too high, decomposition and gas generation of the electrolyte may be accelerated, and the amine is easily oxidized to form a film, so that the impedance is increased, and the cycle is not facilitated. In some embodiments, the first additive is present in an amount of 0.1 to 10% by mass, based on the total mass of the electrolyte. In some embodiments, the first additive is present in an amount of 0.1 to 2% by mass, based on the total mass of the electrolyte. In some embodiments, the first additive is present in an amount of 0.3 to 5% by mass, based on the total mass of the electrolyte.
[ second additive ]
In some embodiments, the electrolyte further comprises a second additive comprising a compound containing a sulfur-oxygen double bond, the compound containing a sulfur-oxygen double bond comprising at least one of the compounds represented by formula (II-a) and formula (II-B);
in the formulae (II-A) and (II-B),
R21and R22Each independently selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R21And R22Can be bonded to form a ring structure;
R23and R24Each independently of the otherIs selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R23And R24Can be bonded to form a ring structure.
When the first additive and the second additive are simultaneously added to the electrolyte, the high-temperature storage performance and the safety performance of the electrochemical device can be further improved. The second additive can form a film on the surfaces of the positive and negative electrode active materials to inhibit the redox decomposition of the electrolyte, and when the second additive is used together with the first additive, the second additive can further inhibit the decomposition of the electrolyte and enhance the protection of the positive and negative electrode active materials, so that the high-temperature storage performance and the safety performance of the electrochemical device are further improved.
In some embodiments, the compound containing a thiooxy double bond comprises at least one of the compounds represented by formula (II-1) to formula (II-22);
in some embodiments, the sulfur oxygen double bond-containing compound is present in an amount of 0.01 to 10% by mass based on the total mass of the electrolyte. When the mass percentage of the compound containing a sulfur-oxygen double bond is within the above range, the high-temperature storage performance and the safety performance of the electrochemical device can be further improved. In some embodiments, the sulfur oxygen double bond-containing compound is present in an amount of 0.1 to 8% by mass based on the total mass of the electrolyte. In some embodiments, the sulfur oxygen double bond-containing compound is present in an amount of 0.1 to 5% by mass based on the total mass of the electrolyte. In some embodiments, the sulfur oxygen double bond-containing compound is present in an amount of 3.5 to 5% by mass based on the total mass of the electrolyte.
[ third additive ]
In some embodiments, the electrolyte further comprises a third additive comprising a boron-containing lithium salt comprising lithium tetrafluoroborate (LiBF)4) At least one of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (lidob).
When the first additive and the third additive are simultaneously added to the electrolyte, the high-temperature storage performance of the electrochemical device can be further improved.
In some embodiments, the boron-containing lithium salt is present in an amount of 0.01 to 3% by mass, based on the total mass of the electrolyte. When the mass percentage of the boron-containing lithium salt is within the above range, the high-temperature storage performance of the electrochemical device can be further improved. In some embodiments, the boron-containing lithium salt is present in an amount of 0.1 to 1% by mass, based on the total mass of the electrolyte.
[ fourth additive ]
In some embodiments, the electrolyte further comprises a fourth additive comprising a P-O bond containing lithium salt comprising lithium difluorophosphate (LiPO)2F2) Lithium difluorobis (oxalato) phosphate (LiDFOP), and lithium tetrafluoro (oxalato) phosphate (LiTFOP).
When the first additive and the fourth additive are simultaneously added to the electrolyte, the high-temperature storage performance of the electrochemical device can be further improved.
In some embodiments, the fourth additive is present in an amount of 0.01 to 3% by mass, based on the total mass of the electrolyte. When the content of the third additive by mass is within the above range, the high-temperature storage performance of the electrochemical device can be further improved. In some embodiments, the fourth additive is present in an amount of 0.1 to 0.5% by mass, based on the total mass of the electrolyte.
[ fifth additive ]
In some embodiments, the electrolyte further comprises a fifth additive comprising a cyclic carbonate compound.
In some embodiments, the cyclic carbonate compound comprises a compound represented by formula (III-a);
in the formula (III-A), R3Selected from substituted or unsubstituted C1-C6Alkylene, substituted or unsubstituted C2-C6Alkenylene, and, when substituted, substituents include halogen, C1-C6Alkyl radical, C2-C6At least one alkenyl group.
When the first additive and the fifth additive are added into the electrolyte at the same time, the stability and flexibility of SEI film formation can be further assisted to be enhanced, so that the protective effect of active substances is further increased, the interface contact probability of the active substances and the electrolyte is reduced, and the impedance increase caused by byproduct accumulation in the circulation process is improved.
In some embodiments, the compound represented by formula (III-A) comprises at least one of the compounds represented by formulae (III-1) to (III-12);
in some embodiments, the second cyclic carbonate compound is present in an amount of 0.01 to 30% by mass, based on the total mass of the electrolyte. In some embodiments, the cyclic carbonate compound is present in an amount of 0.1 to 10% by mass, based on the total mass of the electrolyte.
In some embodiments, the weight ratio between the cyclic carbonate compound and the compound represented by formula (I) is 20:1 to 70: 0.1.
In some embodiments, the cyclic carbonate compound comprises a fluorinated cyclic carbonate compound. In some embodiments, the weight ratio between the fluorinated cyclic carbonate compound and the compound represented by formula (I) is 1:1 to 10: 1.
[ sixth additive ]
In some embodiments, the electrolyte further comprises a sixth additive comprising a polynitrile-based compound comprising at least one of a di-nitrile-based compound and a tri-nitrile-based compound.
In some embodiments, the weight ratio between the polynitrile compound and the compound represented by formula (I) is from 0.01:1 to 1: 1.
[ organic solvent ]
In some embodiments, the electrolyte further comprises an organic solvent. The organic solvent is an organic solvent known in the art to be suitable for an electrochemical device, and for example, a nonaqueous organic solvent is generally used.
In some embodiments, the non-aqueous organic solvent is a carbonate, a carboxylate, an ether, a sulfone, or other aprotic solvent. In some embodiments, the carbonate-based non-aqueous organic solvent comprises at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl ethyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate. In some embodiments, the carboxylic ester non-aqueous organic solvent comprises at least one of ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl propionate, propyl propionate, γ -butyrolactone, 2, 2-difluoroethyl acetate, valerolactone, butyrolactone, 2, 2-difluoroethyl propionate, methyl 3, 3-difluoropropionate, ethyl 4, 4-difluorobutyrate, 3, 3-difluoropropyl acetate, 3, 3-difluoropropyl propionate, 2,2, 2-trifluoroethyl acetate, 2, 2-difluoroethyl formate, 2,2, 2-trifluoroethyl formate, 2,2,3, 3-tetrafluoropropyl propionate. In some embodiments, the ether-based non-aqueous organic solvent comprises at least one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dibutyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran. In some embodiments, the sulfone-based non-aqueous organic solvent comprises at least one of ethyl vinyl sulfone, methyl isopropyl sulfone, isopropyl sec-butyl sulfone, sulfolane.
The non-aqueous organic solvent may be used alone or in a mixture, and when used in a mixture, the ratio of the mixture may be controlled according to the desired performance of the electrochemical device.
[ electrolyte salt ]
In some embodiments, the electrolyte further comprises an electrolyte salt. The electrolyte salt is well known to those skilled in the art and is suitable for use in electrochemical devices, and may be selected for various electrochemical devices. For example, for lithium ion batteries, lithium salts are commonly used as electrolyte salts.
In some embodiments, the lithium salt comprises at least one of an organic lithium salt or an inorganic lithium salt.
In some embodiments, the lithium salt comprises at least one of a fluorine-containing lithium salt, a boron-containing lithium salt, and a phosphorus-containing lithium salt.
In some embodiments, the lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiB (C)2O4)2LiBOB), lithium difluorooxalato borate (LiBF)2(C2O4) LiDFOB), lithium hexafluoroantimonate (LiSbF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium perfluorobutylsulfonate (LiC)4F9SO3) Lithium perchlorate (LiClO)4) Lithium aluminate (LiAlO)2) Lithium aluminum tetrachloride (LiAlCl)4) Lithium bis (sulfonimide) (LiN (C)xF2x+1SO2)(CyF2y+1SO2) Wherein x and y are natural numbers), lithium chloride (LiCl), lithium fluoride (LiF).
In some embodiments, the molar concentration of lithium in the lithium salt is 0.5 to 3mol/L based on the total volume of the electrolyte. In some embodiments, the molar concentration of lithium in the lithium salt is 0.5 to 2mol/L based on the total volume of the electrolyte. In some embodiments, the molar concentration of lithium in the lithium salt is from 0.8mol/L to 1.5mol/L based on the total volume of the electrolyte.
(electrochemical device)
The electrochemical device of the present application is, for example, a primary battery, a secondary battery, a fuel cell, a solar cell, or a capacitor. The secondary battery is, for example, a lithium secondary battery including, but not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
In some embodiments, the electrochemical device is adapted for a charge cutoff voltage of not less than 4.2V.
In some embodiments, the electrochemical device comprises a positive electrode tab, a negative electrode tab, a separator, and an electrolyte as described herein before.
[ Positive electrode sheet ]
The positive electrode tab is a positive electrode tab known in the art that can be used in an electrochemical device. In some embodiments, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer. The positive electrode active material layer is disposed on a surface of the positive electrode current collector.
In some embodiments, the structure of the positive electrode tab is a structure of a positive electrode tab that can be used in an electrochemical device, which is well known in the art.
The application has no special limitation on the compaction density of the positive plate, and can be adjusted according to actual needs. In some embodiments, the positive electrode sheet has a compacted density of 4.15g/cm3。
(i) Positive current collector
In some embodiments, the positive current collector is a metal, such as, but not limited to, aluminum foil.
(ii) Positive electrode active material layer
In some embodiments, the positive electrode active material layer includes a positive electrode active material. The positive electrode active material may be any conventionally known material capable of reversibly intercalating and deintercalating active ions, which is known in the art and can be used as a positive electrode active material for an electrochemical device. In some embodiments, the positive active material includes at least one of a composite oxide of metals of lithium and cobalt, manganese, nickel, or a combination thereof. In some embodiments, the positive active material comprises LiaA1-bWbD2(0.90≤a≤1.8，0≤b≤0.5)、LiaE1-bWbO2-cDc(0.90≤a≤1.8，0<b≤0.5，0≤c≤0.05)、LiE2-bWb04-cDc(0≤b≤0.5，0≤c≤0.05)、LiaNi1-b-cCobWcDα(0.90≤a≤1.8，0≤b≤0.5，0≤c≤0.05，0<α≤2)、LiaNi1-b-cCobWcO2-αTα(0.90≤a≤1.8，0≤b≤0.5，0≤c≤0.05，0<α<2)、LiaNi1-b-cCobWcO2-αT2(0.90≤a≤1.8，0≤b≤0.5，0≤c≤0.05，0<α<2)、LiaNi1-b-cMnbWcDα(0.90≤a≤1.8，0<b≤0.5，0≤c≤0.05，0<α<2)、LiaNi1-b-cMnbWcO2-αTα(0.90≤a≤1.8，0≤b≤0.5，0≤c≤0.05，0<α<2)、LiaNi1-b-cMnbWcO2-αT2(0.90≤a≤1.8，0≤b≤0.5，0≤c≤0.05，0<α<2)、LiaNibEcGdO2(0.90≤a≤1.8，0≤b≤0.9，0≤c≤0.5，0.001≤d≤0.1)、LiaNibCocMndGeO2(0.90≤a≤1.8，0≤b≤0.9，0≤c≤0.5，0≤d≤0.5，0.001≤e≤0.1)、LiaNiGbO2(0.90≤a≤1.8，0.001≤b≤0.1)、LiaCoGbO2(0.90≤a≤1.8，0.001≤b≤0.1)、LiaMnGbO2(0.90≤a≤1.8，0.001≤b≤0.1)、LiaMn2GbO4(0.90≤a≤1.8，0.001≤b≤0.1)、QO2、QS2、LiQS2、V2O5、LiV2O5、LiRO2、LiNiVO4、Li3-fJ2(PO4)3(0≤f≤2)、Li3-fFe2(PO4)3(0≤f≤2)、LiFePO4At least one of; wherein A is Ni, Co, Mn or their combination, W is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or their combination, D is O, F, S,P or a combination thereof, E is Co, Mn or a combination thereof, T is F, S, P or a combination thereof, G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof, Q is Ti, Mo, Mn or a combination thereof, R is Cr, V, Fe, Sc, Y or a combination thereof, J is V, Cr, Mn, Co, Ni, Cu or a combination thereof. In some embodiments, the positive active material is Li (Ni)aCobMncM1-a-b-c)O2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, a + b + c is more than or equal to 0 and less than or equal to 1, and M is Mg, Al, Ti or the combination thereof.
In some embodiments, the positive electrode active material layer includes a first positive electrode active material layer disposed on a surface of the positive electrode current collector and a second positive electrode active material layer disposed on a surface of the first positive electrode active material layer; the first positive electrode active material layer includes a first positive electrode active material, and the second positive electrode active material layer includes a second positive electrode active material. In some embodiments, the first positive electrode active material layer has a thickness of 1 μm to 20 μm. In some embodiments, the second positive electrode active material layer has a thickness of 30 μm to 70 um. In some embodiments, a ratio R of the thickness of the first cathode active material layer to the thickness of the second cathode active material layer satisfies 0.01 ≦ R ≦ 2. In some embodiments, the first positive active material includes at least one of lithium cobaltate, lithium iron phosphate, lithium iron manganese phosphate, sodium iron phosphate, lithium vanadium phosphate, sodium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, a lithium rich manganese based material, lithium nickel cobalt aluminate, or lithium titanate.
In some embodiments, the BET specific surface area of the positive electrode active material particles is not more than 0.5m2(ii) in terms of/g. The BET specific surface area of the positive electrode active material particles is a value obtained by analyzing the surface area of the positive electrode active material powder measured by a nitrogen adsorption method by a BET method (for example, BET1 point method).
In some embodiments, the positive electrode active material layer further comprises a positive electrode binder. The positive electrode binder is a binder known in the art that can be used as a positive electrode active material layer.
In some embodiments, the positive electrode binder comprises at least one of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy, nylon. The positive electrode binder is used to improve the binding properties between positive electrode active material particles and between the positive electrode active material particles and the positive electrode current collector.
In some embodiments, the positive electrode active material layer further includes a positive electrode conductive agent. The positive electrode conductive agent is a conductive agent known in the art that can be used as a positive electrode active material layer.
In some embodiments, the positive electrode conductive agent comprises at least one of natural graphite, artificial graphite, conductive carbon black, conductive paste, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, polyphenylene derivative. In some embodiments, the metal powder comprises at least one of a metal powder of copper, nickel, aluminum, silver. In some embodiments, the metal fibers comprise at least one of metal fibers of copper, nickel, aluminum, silver. The positive electrode conductive agent is used to provide conductivity to the electrode.
In some embodiments, the method for preparing the positive electrode sheet is a method for preparing a positive electrode sheet that can be used for an electrochemical device, which is well known in the art. In some embodiments, in the preparation of the positive electrode slurry, a solvent is generally added, and the positive electrode active material is dissolved or dispersed in the solvent after adding the positive electrode binder and, if necessary, the positive electrode conductive agent and the thickener to prepare the positive electrode slurry. The solvent is evaporated during the drying process. The solvent is a solvent known in the art that can be used as the positive electrode active material layer, and is, for example, but not limited to, N-methylpyrrolidone (NMP). The mixing ratio of the positive electrode active material, the positive electrode binder, and the positive electrode conductive agent in the positive electrode active material layer is not particularly limited, and may be controlled according to the desired electrochemical device performance.
[ negative electrode sheet ]
The negative electrode tab is a negative electrode tab known in the art that may be used in an electrochemical device. In some embodiments, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer. The negative electrode active material layer is disposed on a surface of the negative electrode current collector.
In some embodiments, the structure of the negative electrode sheet is a structure of a negative electrode sheet that may be used in an electrochemical device, as is well known in the art.
The compaction density of the negative electrode plate is not particularly limited and can be adjusted according to actual needs. In some embodiments, the negative electrode sheet has a compacted density of 1.70 to 1.80g/cm3。
(i) Negative current collector
In some embodiments, the negative current collector is a metal such as, but not limited to, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or combinations thereof.
(ii) Negative electrode active material layer
In some embodiments, the anode active material layer includes an anode active material. The negative electrode active material may be any conventionally known material capable of intercalating and deintercalating active ions or any conventionally known material capable of doping and dedoping active ions, which is known in the art and can be used as a negative electrode active material for an electrochemical device.
In some embodiments, the negative electrode active material comprises at least one of a carbon material, lithium metal, and a lithium metal alloy. The carbon material may be selected from various carbon materials known in the art to be used as a carbon-based negative electrode active material for an electrochemical device. In some embodiments, the carbon material comprises at least one of crystalline carbon, amorphous carbon. In some embodiments, the crystalline carbon is natural graphite or artificial graphite. In some embodiments, the crystalline carbon is amorphous, platy, platelet, spherical, or fibrous in shape. In some embodiments, the crystalline carbon is low crystalline carbon or high crystalline carbon. In some embodiments, the low crystalline carbon comprises at least one of soft carbon, hard carbon. In some embodiments, the high crystalline carbon comprises at least one of natural graphite, crystalline graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesophase carbon microbeads, mesophase pitch, high temperature calcined carbon. In some embodiments, the high temperature calcined carbon is petroleum or coke derived from coal tar pitch. In some embodiments, the amorphous carbon comprises at least one of soft carbon, hard carbon, mesophase pitch carbonization products, fired coke. In some embodiments, the negative active material comprises a transition metal oxide. In some embodiments, the lithium metal alloy comprises an alloy of lithium and a metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, Sn.
In some embodiments, the negative electrode active material comprises a silicon system material comprising Si, SiOx (0)<x<2) Si/C composite, Si-Q alloy, Sn, SnOzAt least one of Sn-C composite and Sn-R alloy, wherein Q is at least one of alkali metal, alkaline earth metal, elements from groups 13 to 16, transition element and rare earth element, Q is not Si, R is at least one of alkali metal, alkaline earth metal, elements from groups 13 to 16, transition element and rare earth element, and R is not Sn. In some embodiments, Q and R comprise at least one of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po. In some embodiments, SiOx (0)<x<2) Is a porous negative electrode active material. In some embodiments, the SiOx particles have an average particle size (D)50) Is 1-20 μm. In some embodiments, the average diameter of pores in the SiOx particles is 30-500nm, as measured at the surface. In some embodiments, the SiOx particles have a specific surface area of 5 to 50m2(ii) in terms of/g. In some embodiments, the negative active material comprises SiOx (0)<x<2) And is selected from Li2SiO3、Li4SiO4At least one of (1). In some embodiments, in the Si/C composite, carbon (C) is not agglomerated and dispersed in bulk inside the Si particles, but is uniformly dispersed in an atomic state inside the Si particles. In some embodiments, in the Si/C composite, the molar ratio of C to Si satisfies: 0<C/Si<18. In some embodiments, the weight percent of C is 1 wt% to 50 wt% based on the total weight of the Si/C composite. In some embodiments, the average particle size of the Si/C composite particles is 10-100 μm.
In some embodiments, the negative active material comprises a transition metal oxide. In some embodiments, the transition metal oxide comprises at least one of vanadium oxide, lithium vanadium oxide.
In some embodiments, the negative electrode active material is a carbon material having a BET specific surface area of less than 0.5m2(ii) in terms of/g. The BET specific surface area of the carbon material is a value obtained by analyzing the surface area of the carbon material measured by a nitrogen adsorption method by a BET method (for example, BET1 point method). In some embodiments, the Dv50 of the carbon material is between 5 μm and 35 μm. Wherein Dv50 represents a particle diameter at which the cumulative volume particle diameter distribution of carbon material particles is 50%.
In some embodiments, the anode active material layer further includes an anode binder. The anode binder is a binder known in the art that can be used as an anode active material layer.
In some embodiments, the negative electrode binder is any binder polymer, such as, but not limited to, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, nylon, modified polyacrylic acid. The modified polyacrylic acid is modified polyacrylic acid. In some embodiments, the modified polyacrylic acid is a multiple copolymerized modified polyacrylic acid or a nano modified polyacrylic acid. The negative electrode binder is used to improve binding properties between negative electrode active material particles and between the negative electrode active material particles and a negative electrode current collector.
In some embodiments, the negative electrode active material layer further includes a negative electrode conductive agent. The negative electrode conductive agent is a conductive agent known in the art that can be used as a negative electrode active material layer.
In some embodiments, the negative electrode conductive agent is any conductive agent that does not cause a chemical change, such as, but not limited to, carbon-based materials, such as, but not limited to, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers, metal-based materials, such as, but not limited to, metal powders or metal fibers of copper, nickel, aluminum, silver, etc., conductive polymers, such as, but not limited to, polyphenylene derivatives, or mixtures thereof. The negative electrode conductive agent is used to improve the conductivity of the negative electrode sheet.
In some embodiments, the method of preparing the negative electrode sheet is a method of preparing a negative electrode sheet that may be used for an electrochemical device, which is well known in the art. In some embodiments, in the preparation of the negative electrode slurry, a solvent is generally added, and the negative electrode active material is dissolved or dispersed in the solvent after adding the negative electrode binder and, if necessary, the negative electrode conductive agent and the thickener to prepare the negative electrode slurry. The solvent is evaporated during the drying process. The solvent is a solvent known in the art, such as, but not limited to, water, which can be used as the negative electrode active material layer. The thickener is a thickener known in the art that can be used as the anode active material layer, and is, for example, but not limited to, sodium carboxymethyl cellulose. The mixing ratio of the negative electrode active material, the negative electrode binder, and the thickener in the negative electrode active material layer is not particularly limited, and may be controlled according to the desired electrochemical device performance.
[ isolation film ]
The separator is a separator known in the art that can be used for an electrochemical device, such as, but not limited to, polyolefin-based microporous membranes. In some embodiments, the release film is selected from at least one of Polyethylene (PE), ethylene-propylene copolymer, polypropylene (PP), ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-methyl methacrylate copolymer.
In some embodiments, the polyolefin-based microporous membrane is coated with a coating. In some embodiments, the coating comprises an organic coating and an inorganic coating, wherein the organic coating is selected from the group consisting of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polyimideAmine, acrylonitrile-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, acrylic acid-styrene copolymer, polydimethylsiloxane, sodium polyacrylate, and sodium carboxymethylcellulose, and the inorganic coating is selected from at least one of SiO, acrylonitrile-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, acrylic acid-styrene copolymer, polydimethylsiloxane, sodium polyacrylate, and sodium carboxymethylcellulose2、Al2O3、CaO、TiO2、ZnO2、MgO、ZrO2And SnO2At least one of them. In some embodiments, the coating is a single layer or multiple layers.
In some embodiments, the separator further comprises inorganic particles thereon. In some embodiments, the inorganic particles comprise boehmite, mg (oh)2、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2And SiC. In some embodiments, the inorganic particles have a particle size DV90/DV50 of 1 to 2.
In some embodiments, the separator is a single layer separator or a multilayer separator.
The thickness of the isolation film is not particularly limited, and can be adjusted according to actual needs.
The porosity of the isolating membrane is not particularly limited, and can be adjusted according to actual needs. In some embodiments, the separator has a porosity of 6% to 65%.
[ outer packaging case ]
In some embodiments, the electrochemical device further comprises an overwrap housing. The outer packaging case is a well known outer packaging case in the art that can be used for electrochemical devices and is stable to the electrolyte used, such as, but not limited to, a metal-based outer packaging case.
(electronic device)
The electronic device of the present application is any electronic device such as, but not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable telephone, a portable facsimile, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handy cleaner, a portable CD player, a mini disc, a transceiver, an electronic notebook, a calculator, a memory card, a portable recorder, a radio, a backup power source, a motor, an automobile, a motorcycle, a power-assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large-sized household battery, and a lithium ion capacitor. Note that the electrochemical device of the present application is applicable to an energy storage power station, a marine vehicle, and an air vehicle, in addition to the above-exemplified electronic devices. The air transport carrier device comprises an air transport carrier device in the atmosphere and an air transport carrier device outside the atmosphere.
In some embodiments, the electronic device comprises an electrochemical device as described herein.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
In the following examples and comparative examples, reagents, materials and instruments used were commercially available or synthetically available, unless otherwise specified.
The specific additives used in the electrolyte are as follows:
additive: triethylamine, acetonitrile;
a first additive: 3,3' - (ethane-1, 2-diylbis ((trifluoromethyl) azepinyl)) dipropionitrile (I-3), 3' - ((2- (2- (tert-butyl (2-cyanoethyl) amino) ethyl) azepinyl) dipropionitrile (I-5), 3' - (propane-1, 3-diylbis (azepinyl)) tetrapropionitrile (I-7), 3' - (cyclohexane-1, 4-diylbis (azepinyl)) tetrapropionitrile (I-11), 3' - ((((((((2-cyanoethyl) azepinyl) bis (ethane-2, 1-diyl)) bis (azepinyl)) tetrapropionitrile (I-12), 4,7,10, 13-tetrakis (2-cyanoethyl) -4,7,10, 13-tetraazahexadecylcanecarbonitrile (I-14), 4,8,12,16, 20-pentakis (2-cyanoethyl) -4,8,12,16, 20-pentaza (I-16):
a second additive: 1, 3-propane sultone (II-12), vinyl sulfate (II-18), methylene methanedisulfonate (II-21):
a third additive: lithium tetrafluoroborate (LiBF)4) Lithium difluorooxalato borate (liddob);
a fourth additive: lithium difluorophosphate (LiPO)2F2) Lithium tetrafluoro oxalate phosphate (litfo).
Organic solvent: ethylene carbonate (abbreviated EC), propylene carbonate (abbreviated PC), diethyl carbonate (abbreviated DEC), ethyl propionate (abbreviated EP), propyl propionate (abbreviated PP);
lithium salt: lithium hexafluorophosphate (LiPF)6)。
Among them, the compound represented by formula (I) in the present application is commercially available, or can be synthesized by a preparation method known and conventional in the art, or can also be synthesized by the following preparation method, taking the compound represented by formula (I-12) as an example, the specific synthesis steps are:
dissolving diethylenetriamine (10.3g, 0.1mol) in 800mL of water, dropwise adding acrylonitrile (53.1g, 1mol) into the system at room temperature, continuing stirring for 1h after the dropwise addition is finished, and then raising the temperature to 110 ℃ for reaction for 1.5 h. Cooled to room temperature, filtered and purified by silica gel column to give 23.9g (65%).1HNMR(400MHz,CD3CN,ppm):δ2.78—2.85(m,10H,CH2CN),2.59—2.62(m,8H,N-CH2-CH2-N),2.50(t,N-CH2-CH2-CN,J＝6.8Hz).ESI-HRMS:m/z Calcd for C19H28N8+H+:369.2510,found:369.2516。
The compounds represented by the formulae (I-1) to (I-16) can be obtained by a synthesis method similar to that for the compound represented by the formula (I-12), and the reactants of the synthesis reaction are adjusted.
The lithium ion batteries of examples 1 to 52 and comparative examples 1 to 2 were each prepared as follows
(1) Preparation of the electrolyte
At water content<In a 10ppm argon atmosphere glove box, uniformly mixing non-aqueous organic solvents EC, PC, DEC, EP and PP according to the mass ratio of 1:1:1:1:1, and then fully drying lithium salt LiPF6Dissolving in the non-aqueous organic solvent, finally adding a certain mass of additive, and fully mixing to obtain the electrolyte with the lithium salt concentration of 1 mol/L.
(2) Preparation of positive plate
Mixing anode active material LCO (molecular formula is LiCoO)2) The conductive carbon black, the conductive slurry and the adhesive polyvinylidene fluoride (PVDF) are fully stirred and mixed in a proper amount of N-methyl pyrrolidone (NMP) solvent according to the weight ratio of 97.9:0.4:0.5:1.2 to form uniform anode slurry; coating the slurry on a positive current collector Al foil, drying and cold pressing to obtain a positive plate, wherein the positive electrode compaction density is 4.15g/cm3。
(3) Preparation of the separator
The single-layer Polyethylene (PE) porous polymer film is used as an isolating film, the thickness of the isolating film is 5 microns, the porosity of the isolating film is 39%, and the inorganic coating is Al2O3The organic particles are polyvinylidene fluoride.
(4) Preparation of negative plate
Fully stirring and mixing a negative electrode active material graphite, a binder Styrene Butadiene Rubber (SBR) and a thickener sodium carboxymethyl cellulose (CMC) in a proper amount of deionized water solvent according to a weight ratio of 97.4:1.4:1.2 to form uniform negative electrode slurry; coating the negative electrode slurry on a negative electrode current collector Cu foil, drying and cold pressing to obtain a negative electrode piece, wherein the compaction density of the negative electrode piece is 1.80g/cm3。
(5) Preparation of lithium ion battery
Stacking the prepared positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate to play an isolating role, and then winding to obtain the bare cell; and (3) placing the bare cell in an outer packaging foil, leaving a liquid injection port, injecting the prepared electrolyte from the liquid injection port, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
In examples 1 to 52 and comparative examples 1 to 2, the kinds and contents of additives in the electrolytes used are shown in tables 1 and 2, wherein the contents of the respective additives are weight percentages calculated based on the total mass of the electrolyte.
TABLE 1 kinds and contents of additives added in examples 1-29 and comparative examples 1-2
TABLE 2 types and amounts of additives added in examples 30-52
The following tests were performed on the lithium ion batteries of examples 1 to 52 and comparative examples 1 to 2, respectively
(1) High temperature storage Performance test
The cell was charged at 25 ℃ to 4.45V at a constant current of 0.5C, then charged at constant voltage to a current of 0.05C, and the thickness of the lithium ion cell at this time was measured and recorded as d0(ii) a And then placing the lithium ion battery in an oven at 85 ℃, taking out the lithium ion battery after 24 hours, and testing the thickness of the lithium ion battery at the moment and recording the thickness as d.
Thickness expansion ratio (%) after high-temperature storage at 85 ℃ for 24 hours (d-d)0)/d0×100％。
(2) Hot box test
Charging the lithium ion battery to 4.45V at a constant current of 0.5C, then charging the lithium ion battery to 0.05C at a constant voltage of 4.45V, then placing the lithium ion battery in a constant temperature box at 25 +/-5 ℃, standing for 60min, checking the appearance of the lithium ion battery at the moment and taking a picture; then, the incubator was raised to 130 ± 2 ℃ at a rate of 5 ± 2 ℃/min and maintained for 60min, and the appearance of the lithium ion battery at this time was checked again and photographed. 10 lithium ion batteries were tested in parallel and the number of passed lithium ion batteries was recorded using "no fire, no explosion" as the criterion for passage.
(3) Cycle performance test
Charging the battery to 4.45V at 25 deg.C at 0.7C, further charging to 0.05C at 4.45V at constant voltage, and then discharging to 3.0V at 1C; and the procedures of 0.7C charging and 1C discharging are carried out circularly for 800 circles, and the discharge capacity of the 2 nd circle is marked as C0And the discharge capacity at the 800 th cycle is marked as C1。
Capacity retention (%) of 800 cycles at room temperature ═ C1/C0×100％。
The test results of the lithium ion batteries of examples 1 to 52 and comparative examples 1 to 2 are shown in tables 3 and 4
TABLE 3 results of Performance test of the lithium ion batteries of examples 1 to 29 and comparative examples 1 to 2
Table 4 results of performance testing of the lithium ion batteries of examples 4, 30-52
The lithium ion batteries of examples 53 to 55 and comparative examples 3 to 4 were each prepared as follows
(1) Preparation of the electrolyte
At water content<In a 10ppm argon atmosphere glove box, uniformly mixing non-aqueous organic solvents EC, PC, DEC, EP and PP according to the mass ratio of 1:1:1:1:1, and then fully drying lithium salt LiPF6Dissolving in the non-aqueous organic solvent, finally adding a certain mass of additive, and fully mixing to obtain the electrolyte with the lithium salt concentration of 1 mol/L.
(2) Preparation of positive plate
Mixing anode active material LCO (molecular formula is LiCoO)2) The conductive carbon black, the conductive slurry and the adhesive polyvinylidene fluoride (PVDF) are fully stirred and mixed in a proper amount of N-methyl pyrrolidone (NMP) solvent according to the weight ratio of 97.9:0.4:0.5:1.2 to form uniform anode slurry; coating the slurry on a positive current collector Al foil, drying and cold pressing to obtain a positive plate, wherein the positive electrode compaction density is 4.15g/cm3。
(3) Preparation of the separator
The single-layer Polyethylene (PE) porous polymer film is used as an isolating film, the thickness of the isolating film is 5 microns, the porosity of the isolating film is 39%, and the inorganic coating is Al2O3The organic particles are polyvinylidene fluoride.
(4) Preparation of negative plate
Fully stirring and mixing a negative electrode active material graphite, a negative electrode active material silicon material, a thickener sodium carboxymethyl cellulose (abbreviated as CMC) and modified polyacrylic acid in a proper amount of deionized water solvent according to a weight ratio of 87:10:0.6:2.4 to form uniform negative electrode slurry; coating the negative electrode slurry on a negative electrode current collector Cu foil, drying and cold pressing to obtain a negative electrode piece, wherein the compaction density of the negative electrode piece is 1.70g/cm3。
(5) Preparation of lithium ion battery
Stacking the prepared positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate to play an isolating role, and then winding to obtain the bare cell; and (3) placing the bare cell in an outer packaging foil, leaving a liquid injection port, injecting the prepared electrolyte from the liquid injection port, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
In examples 53 to 55 and comparative examples 3 to 4, specific kinds of silicon materials used as the negative electrode active material, and kinds and contents of additives in the electrolyte used are shown in table 5, wherein the contents of the respective additives are weight percentages calculated based on the total mass of the electrolyte.
The lithium ion batteries of examples 53 to 55 and comparative examples 3 to 4 were subjected to the following tests, respectively
(1) Hot box test
Charging the lithium ion battery to 4.45V at a constant current of 0.5C, then charging the lithium ion battery to 0.05C at a constant voltage of 4.45V, then placing the lithium ion battery in a constant temperature box at 25 +/-5 ℃, standing for 60min, checking the appearance of the lithium ion battery at the moment and taking a picture; then, the incubator was raised to 130 ± 2 ℃ at a rate of 5 ± 2 ℃/min and maintained for 60min, and the appearance of the lithium ion battery at this time was checked again and photographed. 10 lithium ion batteries were tested in parallel and the number of passed lithium ion batteries was recorded using "no fire, no explosion" as the criterion for passage.
(2) High temperature storage Performance test
The cell was charged at 25 ℃ to 4.45V at a constant current of 0.5C, then charged at constant voltage to a current of 0.05C, and the thickness of the lithium ion cell at this time was measured and recorded as D0(ii) a And then placing the lithium ion battery in a 60 ℃ oven, taking out the lithium ion battery after 30 days, and testing the thickness of the lithium ion battery at the moment and recording the thickness as D.
Thickness expansion ratio (%) after 30 days of high temperature storage at 60 ℃ [ (% D-D) ]0)/D0×100％。
TABLE 5 parameters for examples 53-55 and comparative examples 3-4
| Numbering | Kind of additive | Content (wt%) | Kind of silicon material as negative electrode active material |
| Comparative example 3 | - | - | Silicon oxygen |
| Comparative example 4 | - | - | Silicon carbon |
| Example 53 | I-16 | 0.3 | Silicon oxygen |
| Example 54 | I-7 | 0.5 | Silicon carbon |
| Example 55 | I-16 | 0.3 | Silicon carbon |
TABLE 6 results of Performance test of the lithium ion batteries of examples 53 to 55 and comparative examples 3 to 4
| Numbering | Number of lithium ion batteries passed by hot box test | Thickness expansion ratio (%) |
| Comparative example 3 | 0 | 100％ |
| Comparative example 4 | 0 | 100％ |
| Example 53 | 4 | 17.60％ |
| Example 54 | 9 | 14.20％ |
| Example 55 | 7 | 15.00％ |
As can be seen from the analysis of the relevant data in tables 1 to 4, the lithium ion battery can have better high-temperature storage performance and safety performance when the compound represented by the formula (I) is added. Although the compound represented by formula (I) has amine and cyano functional groups, it can be seen from the data in Table 3 that when an amine-containing compound and a cyano-containing compound are added simultaneously, the improvement effect is significantly inferior to that of the compound represented by formula (I) directly added, since amine-based substances are relatively easily consumed by oxidation and do not exert a continuous protection effect, but if combined with nitrile-based functional groups on the same molecule, the cyano functional groups can interact with transition metals, and the stability of the film after amine oxidation film formation can be maintained. And if two functional groups are present in the two compounds respectively, the synergistic effect of the compound represented by the formula (I) is not obtained, and the improvement effect is not obtained.
According to the analysis of the relevant data of examples 1 to 14, it can be seen that when the compound represented by formula (I) is contained in an amount of 0.3% to 10% by mass, the improvement effect on the high-temperature storage performance and the safety performance of the lithium ion battery is better. When the mass percentage of the compound represented by the formula (I) is 3-10%, the performance of the lithium ion battery can be further improved.
According to the analysis of the relevant data of comparative example 1 and examples 4 and 9 to 29, it is understood that when the compound containing a sulfur-oxygen double bond as described herein is further added to the electrolyte solution to which the compound represented by formula (I) is added, the high-temperature storage performance and safety performance of the lithium ion battery can be further improved. The reason is that, on the one hand, the compound containing the sulfoxy double bond described in the present application has a strong oxidation resistance and is not easily oxidized on the surface of the positive electrode, and on the other hand, in the case of lithium precipitation at the negative electrode, the compound containing the sulfoxy double bond described in the present application can be reduced on the surface of the metal lithium to form a protective film, so that decomposition heat generation of the metal lithium and the electrolyte can be inhibited, and the protection of the active material can be further enhanced. When the mass percentage of the compound containing the sulfur-oxygen double bond is 3.5-5%, the improvement effect on the high-temperature storage performance and the safety performance of the lithium ion battery is better.
According to the analysis of the relevant data of comparative example 1 and examples 4, 9 to 14, and 30 to 40, it is understood that when the compound containing a sulfur-oxygen double bond as described herein is further added to the electrolyte solution to which the compound represented by formula (I) is added, the high-temperature storage performance of the lithium ion battery can be further improved. The reason is that the compound containing a thiooxy double bond described herein has higher thermal stability than lithium hexafluorophosphate, and can form a protective film containing a thiooxy double bond on the surface of the positive and negative electrodes, and reduce the reaction of a film forming additive (FEC, for example, a compound represented by formula (I) or a compound containing a thiooxy double bond described herein) with the negative electrode, thereby suppressing gas generation and further improving the high-temperature storage performance of the lithium ion battery.
According to the analysis of the relevant data of comparative example 1 and examples 4, 9 to 14, and 41 to 52, it is understood that when the lithium salt having a P — O bond as described herein is further added to the electrolyte solution to which the compound represented by formula (I) is added, the high-temperature storage performance of the lithium ion battery can be further improved. The reason is that the lithium salt containing the P-O bond can form a film on the positive electrode, and the contact between the electrolyte and the positive electrode is reduced, so that the effect of inhibiting gas generation is achieved, and the high-temperature storage performance of the lithium ion battery is further improved.
As can be seen from the analysis of the relevant data in tables 5 to 6, the compound represented by formula (I) is suitable for a lithium ion battery with a negative electrode active material of silicon oxygen or silicon carbon, and can significantly improve the safety performance and high-temperature storage performance of a silicon-based lithium ion battery, probably because the amine functional group in the compound of formula (I) can slow down the consumption of nitrile substances by a silicon negative electrode, thereby enhancing the protection of a positive electrode interface; on the other hand, the compound of the formula (I) can adsorb hydrofluoric acid and inhibit the decomposition of an SEI film.
The above detailed description describes exemplary embodiments, but is not intended to limit the combinations explicitly disclosed herein. Thus, unless otherwise specified, various features disclosed herein can be combined together to form a number of additional combinations that are not shown for the sake of brevity.
Claims (10)
1. An electrolytic solution, comprising a compound represented by the formula (I);
in the formula (I), the compound represented by the formula (I),
A1and A2Each independently selected from any one of structural formulas shown in a formula (I-A), a formula (I-B) and a formula (I-C);
wherein the content of the first and second substances,
represents a binding site to an adjacent atom;
R11、R12、R14each independently selected from the group consisting of a covalent bond, substituted or unsubstituted C1-C10Alkylene, substituted or unsubstituted C2-C10Alkenylene, substituted or unsubstituted C2-C10Alkynylene, substituted or unsubstituted C3-C10Alkenylene, substituted or unsubstituted C6-C10Arylene, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
R13selected from substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alkenyl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C3-C10Any one of alicyclic hydrocarbon groups, and when substituted, the substituent is halogen;
m is selected from 0 or 1;
n is an integer of 2 to 6, and, when n is 2 or more, 2 or more R12The same or different.
2. The electrolyte of claim 1,
the compound represented by the formula (I) comprises at least one of the compounds represented by the formulae (I-1) to (I-16);
3. the electrolyte of claim 1,
the mass percentage content of the compound represented by formula (I) is 0.01% to 10% based on the total mass of the electrolyte.
4. The electrolyte of claim 3,
the mass percentage content of the compound represented by formula (I) is 0.01 to 2% based on the total mass of the electrolyte.
5. The electrolytic solution according to claim 1, further comprising a compound containing a sulfur-oxygen double bond, the compound containing a sulfur-oxygen double bond comprising at least one of compounds represented by formula (II-a) and formula (II-B);
in the formulae (II-A) and (II-B),
R21and R22Each independently selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R21And R22Can be bonded to form a ring structure;
R23and R24Each independently selected from substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C2-C10Alkynyl, substituted or unsubstituted C3-C10Alicyclic group, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C1-C6And, when substituted, the substituents include at least one of halogen and heteroatom-containing functional groups, wherein R23And R24Can be bonded to form a ring structure.
6. The electrolyte of claim 5,
the compound containing a sulfur-oxygen double bond includes at least one of compounds represented by the formulae (II-1) to (II-22);
the sulfur-oxygen double bond-containing compound is contained in an amount of 0.01 to 10% by mass based on the total mass of the electrolyte.
7. The electrolyte of claim 1, further comprising a boron-containing lithium salt comprising at least one of lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate;
the mass percentage of the boron-containing lithium salt is 0.01 to 3 percent based on the total mass of the electrolyte.
8. The electrolyte of claim 1, further comprising a lithium salt containing a P-O bond, the lithium salt containing a P-O bond comprising at least one of lithium difluorophosphate, lithium difluorobis-oxalato phosphate, lithium tetrafluorooxalato phosphate;
the content of the lithium salt having a P-O bond is 0.01 to 3% by mass based on the total mass of the electrolyte.
9. An electrochemical device comprising a positive electrode sheet, a negative electrode sheet, a separator, and the electrolyte according to any one of claims 1 to 8.
10. An electronic device comprising the electrochemical device of claim 9.
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