CN117613389B - Electrolyte additive, electrolyte for lithium ion battery and lithium ion battery - Google Patents
Electrolyte additive, electrolyte for lithium ion battery and lithium ion battery Download PDFInfo
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- CN117613389B CN117613389B CN202410098523.8A CN202410098523A CN117613389B CN 117613389 B CN117613389 B CN 117613389B CN 202410098523 A CN202410098523 A CN 202410098523A CN 117613389 B CN117613389 B CN 117613389B
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- electrolyte
- lithium
- substituent
- additive
- lithium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 94
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 28
- -1 benzotriazole phosphate compound Chemical class 0.000 claims abstract description 96
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 125000001424 substituent group Chemical group 0.000 claims abstract description 49
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 53
- 239000012964 benzotriazole Substances 0.000 claims description 53
- 239000010452 phosphate Substances 0.000 claims description 53
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 8
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 150000005678 chain carbonates Chemical class 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 claims description 3
- DCWYVUZDHJMHRQ-UHFFFAOYSA-M lithium;ethyl sulfate Chemical compound [Li+].CCOS([O-])(=O)=O DCWYVUZDHJMHRQ-UHFFFAOYSA-M 0.000 claims description 3
- ALYPSPRNEZQACK-UHFFFAOYSA-M lithium;methyl sulfate Chemical compound [Li+].COS([O-])(=O)=O ALYPSPRNEZQACK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 abstract description 23
- 150000003624 transition metals Chemical class 0.000 abstract description 23
- 239000007789 gas Substances 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 16
- 230000000242 pagocytic effect Effects 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 12
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 11
- 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 abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 125000005842 heteroatom Chemical group 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 229910001453 nickel ion Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 230000005501 phase interface Effects 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical group P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- PQYORWUWYBPJLQ-UHFFFAOYSA-N buta-1,3-diene;sulfurous acid Chemical compound C=CC=C.OS(O)=O PQYORWUWYBPJLQ-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical group C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 2
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 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 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
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- 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 provides an electrolyte additive, electrolyte for a lithium ion battery and the lithium ion battery. The electrolyte additive comprises a benzotriazole phosphate compound with a structure shown in a formula I: In the formula I, R 1 and R 2 are respectively and independently selected from any one of a first substituent and a second substituent, and R 3 and R 4 are respectively and independently selected from any one of a hydrogen atom, a first substituent and a second substituent. The benzotriazole phosphate compound in the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, so that the benzotriazole phosphate compound can be coordinated with high-valence transition metal nickel, manganese, iron and the like in situ, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, thereby avoiding the generation of gas by oxidative decomposition of electrolyte, and effectively solving the problem of gas generation of the battery in the high-voltage charge-discharge process.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an electrolyte additive, an electrolyte for a lithium ion battery and the lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density and the like, and is the main development and application direction of the power battery and the energy storage product at present.
At present, the method for improving the energy density of the lithium battery is to improve the proportion of nickel in the positive electrode material on one hand and to improve the upper limit voltage of the positive electrode material on the other hand. However, the increase of nickel content or the increase of upper limit voltage of operation can cause the increase of thermal instability and surface activity of the positive electrode material, so that transition metal nickel and manganese ions are dissolved out, and the dissolved nickel and manganese ions can continuously react with organic components in the electrolyte, thereby accelerating the consumption of the electrolyte; in addition, gas is generated in the reaction process, so that the impedance of the anode of the battery is increased, the problems of cycle attenuation and the like are caused, the service life of the battery is shortened, and the safety problem is caused; meanwhile, the structural change and surface activity enhancement of the anode material can accelerate the side reaction of the anode interface, so that the anode structure is damaged, and the anode material is invalid. It is therefore necessary to construct a stable positive electrode/electrolyte interface.
Therefore, the problem of the dissolution of transition metal nickel and manganese ions in the electrolyte seriously affects the service life and the safety of the lithium ion battery, and the problem of the dissolution of the transition metal nickel and manganese ions in the electrolyte is solved, so that the method has an important influence on improving the performance and the reliability of the lithium ion battery.
Disclosure of Invention
The invention mainly aims to provide an electrolyte additive, an electrolyte for a lithium ion battery and the lithium ion battery, so as to solve the problem that transition metal nickel and manganese ions in the electrolyte dissolve out to influence the battery performance in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided an electrolyte additive comprising a benzotriazole-based phosphate compound having a structure of formula I,
I is a kind of
In the formula I, R 1 and R 2 are respectively and independently selected from any one of a first substituent and a second substituent, and R 3 and R 4 are respectively and independently selected from any one of a hydrogen atom, the first substituent and the second substituent; the first substituent includes a halogen atom, a cyano group, a carboxylate group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms; the second substituent includes a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 6 carbon atoms, an unsaturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms and a silane group having 1 to 6 carbon atoms; when R 1 or R 2 or R 3 or R 4 is selected from the second substituent, the hydrogen atom of the second substituent may be substituted with the first substituent.
Further, R 1 and R 2 are each independently selected from any one of the second substituents, preferably, R 1 and R 2 are the same;
And/or R 3 and R 4 are each independently selected from any one of a hydrogen atom and a first substituent, preferably, R 3 and R 4 are the same.
Further, the second substituent is any one of a linear alkyl group having 2 to 3 carbon atoms, a linear alkoxy group having 2 to 3 carbon atoms, and a silane group having 3 to 6 carbon atoms.
Further, the first substituent is any one of a halogen atom and a cyano group.
Further, the electrolyte additive also comprises a negative electrode film-forming additive, wherein the negative electrode film-forming additive comprises any one or more of fluoroethylene carbonate, vinylene carbonate, ethylene sulfate, propylene sulfate, 4-methyl ethylene sulfate, vinyl ethylene carbonate, 4-ethyl ethylene sulfate, 1, 3-propane sultone, vinyl ethylene sulfite, tri (trimethylsilyl) borate and triallyl isocyanate;
preferably, the negative electrode film-forming additive includes any two or more of fluoroethylene carbonate, ethylene sulfate, vinylene carbonate, triallyl isocyanurate, and 1, 3-propane sultone.
According to another aspect of the present application, there is provided an electrolyte for a lithium ion battery, the electrolyte comprising: lithium salt, organic solvent and additive, the additive is any electrolyte additive.
Further, the additive accounts for 0.2-5 wt% of the mass of the electrolyte for the lithium ion battery.
Further, the benzotriazole phosphate compound with the structure shown in the formula I accounts for 0.1-2wt% of the mass of the electrolyte for the lithium ion battery;
Preferably, the benzotriazole phosphate compound with the structure shown in the formula I accounts for 0.2-1 wt% of the mass of the electrolyte for the lithium ion battery.
Further, the lithium salt includes any one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorobisoxalato phosphate, lithium difluorosulfonimide, lithium bistrifluoromethane sulfonyl imide, lithium difluorophosphate, lithium tetrafluorophosphate, potassium difluorosulfonimide, 4, 5-dicyano-2-trifluoromethyl-imidazole lithium, lithium methylsulfate, lithium ethylsulfate and lithium bis (nonafluorobutylsulfonyl) imide;
and/or the organic solvent comprises any one or more of chain carbonate and cyclic carbonate;
Preferably, the lithium salt includes any three or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorobisoxalato phosphate, lithium difluorosulfonimide, lithium difluorophosphate and lithium bis (nonafluorobutylsulfonyl) imide; more preferably, the lithium salt comprises lithium hexafluorophosphate;
preferably, the chain carbonate is selected from any one or more of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and dipropyl carbonate;
preferably, the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate.
According to still another aspect of the present application, there is provided a lithium ion battery including: positive plate, negative plate, diaphragm and electrolyte, wherein, the electrolyte is the electrolyte for the lithium ion battery of any one of the above-mentioned.
The electrolyte additive provided by the application has the following beneficial effects:
1. The benzotriazole phosphate compound serving as the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and has P, O, N and other heteroatoms in a molecular structure serving as byproducts generated after the phagocytic agent, so that the benzotriazole phosphate compound can be coordinated with high-valence transition metal nickel, manganese, iron and the like in situ, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, so that the problem that the electrolyte is oxidized and decomposed to generate gas is avoided, the problem that the battery generates gas in the high-voltage charge and discharge process is effectively solved, the cycle performance of the battery in the high-voltage charge and discharge process is improved, the service life of the battery is prolonged, and the safety performance of the battery is improved.
2. The phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and can be combined with hexafluorophosphate ions on the other hand when lithium salt of electrolyte comprises lithium hexafluorophosphateTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery.
3. The additive has lower oxidation potential, can form a compact and stable passivation film on the surface of the positive electrode in the first charging process, can effectively inhibit the oxidative decomposition of the organic solvent in the electrolyte on the surface of the positive electrode, and effectively solves the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed by the background art of the application, the prior art has the problem that the battery performance is affected by the dissolution of transition metal nickel and manganese ions in the electrolyte in the high-voltage charge and discharge process, and in order to solve the problem, the application provides an electrolyte additive, an electrolyte for a lithium ion battery and the lithium ion battery.
According to an exemplary embodiment of the present application, there is provided an electrolyte additive including a benzotriazole-based phosphate compound having the structure of formula I:
I is a kind of
In the formula I, R 1 and R 2 are respectively and independently selected from any one of a first substituent and a second substituent, and R 3 and R 4 are respectively and independently selected from any one of a hydrogen atom, the first substituent and the second substituent; the first substituent includes a halogen atom, a cyano group, a carboxylic acid ester group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms; the second substituent includes a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxy group having 1 to 6 carbon atoms, an unsaturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms and a silane group having 1 to 6 carbon atoms; wherein the hydrogen atom of the second substituent may be substituted with the first substituent. For example, when R 1 or R 2 or R 3 or R 4 is selected from the second substituent, a hydrogen atom in the second substituent may be substituted with the first substituent.
Firstly, the benzotriazole phosphate compound in the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and on the other hand, the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, so that the in-situ coordination can be carried out on the byproducts and high-valence transition metal nickel, manganese, iron and the like, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, thereby avoiding the generation of gas by oxidative decomposition of electrolyte, effectively solving the problem of gas generation of the battery in the high-voltage charge and discharge process, improving the cycle performance of the battery in the high-voltage charge and discharge process, prolonging the service life of the battery and improving the safety performance of the battery. Furthermore, the phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and on the other hand, when lithium salt of electrolyte comprises lithium hexafluorophosphate, the phosphoramide framework can be prepared by combining with hexafluorophosphate ionsTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery. Further, the additive has lower oxidation potential, a compact and stable passivation film can be formed on the surface of the positive electrode in the first charging process, the oxidative decomposition of the organic solvent of the electrolyte on the surface of the positive electrode can be effectively inhibited, and the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process is effectively solved.
In some embodiments of the present application, R 1 and R 2 are each independently selected from any one of the second substituents, which is to be noted that, when R 1 and R 2 are the second substituents, it is advantageous to further promote the coordination of the by-product generated after the reaction of the benzotriazole-based phosphate compound having the structure of formula I as a phagocytic agent with the higher transition metal nickel, manganese, iron, etc., so as to promote the inhibition of the ion elution of the transition metal nickel, manganese, iron.
In some embodiments of the present application, R 3 and R 4 are each independently selected from any of the hydrogen atoms and the first substituents described above, i.e., R 3 is selected from a hydrogen atom or a first substituent, and R 4 is selected from a hydrogen atom or a first substituent, and electrolyte additives containing the same are more effective.
When R 3 and/or R 4 is any one of an ether group containing 1-6 carbon atoms and an aryl group containing 6-18 carbon atoms, the coordination of byproducts generated after the benzotriazole-based phosphate compound with the structure of formula I is reacted as a phagocytic agent with high-valence transition metals such as nickel, manganese and iron is promoted, so that the inhibition effect on the dissolution of transition metal nickel, manganese and iron ions is promoted. When R 3 or R 4 is any one of halogen atom, cyano and carboxylic ester group containing 1-6 carbon atoms, the benzotriazole phosphate compound with the structure shown in the formula I can better phagocytize HF and water and has better water and acid removal effects.
In some embodiments of the application, preferably, R 1、R2 are the same; and/or R 3、R4 are the same, i.e., R 1 and R 2 are the same groups, and/or R 3 and R 4 are the same groups.
It should be noted that R 1、R2 is the same; and/or, when R 3、R4 is the same, the preparation process of the benzotriazole phosphate compound with the structure shown in the formula I is simpler, and the material is cheaper and more available.
In some preferred embodiments of the present application, the first substituent is any one of a halogen atom and a cyano group, and the corresponding benzotriazole-based phosphate compound can play a good role in promoting the application of the electrolyte additive, whether being used as a substituent of a hydrogen atom on the second substituent or being used as R 3 or R 4.
In some preferred embodiments of the present application, the second substituent is any one of a linear alkyl group having 2 to 3 carbon atoms, a linear alkoxy group having 2 to 3 carbon atoms, and a silyl group having 3 to 6 carbon atoms, and the corresponding benzotriazole-based phosphate compound improves significantly as an electrolyte additive when R 1 to R 4, particularly R 1 and R 2 are selected from the above groups.
In some exemplary embodiments of the present application, the benzotriazole-based phosphate compound having the structure of formula I is any one or more of the following compounds:
(denoted as B1),/> (Denoted as B2),
(Denoted as B3),/>(Denoted as B4),
(Denoted as B5).
To further enhance the performance of the electrolyte additive, in some embodiments of the application, the electrolyte additive further comprises a negative film-forming additive. The specific kind of the negative electrode film-forming additive may be selected in the prior art, and the present application is not limited. In some embodiments of the application, the film-forming additive comprises any one or more of fluoroethylene carbonate, vinylene carbonate, ethylene sulfate, propylene sulfate, 4-methyl ethylene sulfate, vinyl ethylene carbonate, 4-ethyl ethylene sulfate, 1, 3-propane sultone, vinyl ethylene sulfite, tri (trimethylsilyl) borate, and triallyl isocyanurate.
In some preferred embodiments of the present application, the negative electrode film-forming additive includes any two or more of fluoroethylene carbonate (FEC), ethylene sulfate (DTD), vinylene Carbonate (VC), triallyl isocyanurate (u-v), and 1, 3-Propane Sultone (PS), and can exert a synergistic effect with the above benzotriazole-based phosphate compound, further improving the cycle performance and stability of the battery.
According to another exemplary embodiment of the present application, there is provided an electrolyte for a lithium ion battery including: lithium salt, organic solvent and additive, the additive is any electrolyte additive.
The benzotriazole phosphate compound in the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, so that the in-situ coordination can be carried out on the byproducts with high-valence transition metal nickel, manganese, iron and the like, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, thereby avoiding the generation of gas by oxidative decomposition of electrolyte, effectively solving the problem of gas generation of the battery in the high-voltage charge and discharge process, improving the cycle performance of the battery in the high-voltage charge and discharge process, prolonging the service life of the battery and improving the safety performance of the battery. Furthermore, the phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and on the other hand, when lithium salt of electrolyte comprises lithium hexafluorophosphate, the phosphoramide framework can be prepared by combining with hexafluorophosphate ionsTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery. Further, the additive has lower oxidation potential, a compact and stable passivation film can be formed on the surface of the positive electrode in the first charging process, the oxidative decomposition of the organic solvent of the electrolyte on the surface of the positive electrode can be effectively inhibited, and the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process is effectively solved.
In order to better play the role of the additive, in some preferred embodiments of the application, the additive accounts for 0.2wt% to 5wt% of the mass of the electrolyte for the lithium ion battery.
In some embodiments of the present application, in order to further improve the performance of the electrolyte, preferably, the benzotriazole-based phosphate compound having the structure of formula I in the additive accounts for 0.1wt% to 2wt% of the electrolyte for lithium ion batteries, and more preferably, the benzotriazole-based phosphate compound having the structure of formula I accounts for 0.2 wt wt% to 1wt% of the electrolyte for lithium ion batteries.
The lithium salt in the above-mentioned electrolyte for lithium ion batteries may be selected from the prior art, and examples of the lithium salt include, but are not limited to, any one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorobisoxalato phosphate, lithium difluorosulfonimide, lithium bistrifluoromethane sulfonimide, lithium difluorophosphate, lithium tetrafluorophosphate, potassium difluorosulfonimide, 4, 5-dicyano-2-trifluoromethyl-imidazole lithium, lithium methylsulfate, lithium ethylsulfate and lithium bis (nonafluorobutylsulfonyl) imide.
In some preferred embodiments of the present application, the lithium salt includes any three or more of lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4 ), lithium difluorobis (oxalato) phosphate (LiDFOP), lithium difluorosulfonimide (LiFSI), lithium difluorophosphate (LiDFP/LiPO 2F2) and lithium bis (nonafluorobutylsulfonyl) imide (npi), and the additive of the present application can better promote uniform growth of the CEI/SEI film, increase the migration number of Li +, inhibit the generation of harmful substances, and further improve the cycle life and safety of the high nickel high voltage battery. More preferably, the lithium salt comprises lithium hexafluorophosphate, and when lithium hexafluorophosphate (LiPF 6) is contained in the lithium salt, the benzotriazole-based phosphate compound in the additive of the present application is incorporated by bindingThe anions inhibit the generation of harmful substances and further improve the cycle life and the safety of the battery.
The above organic solvent may also be selected from the prior art, such as any one or more of chain carbonates and cyclic carbonates. Preferably, the chain carbonate is selected from any one or more of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and dipropyl carbonate; preferably, the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate.
According to still another exemplary embodiment of the present application, there is provided a lithium ion battery including: positive plate, negative plate, diaphragm and electrolyte, wherein, the electrolyte is the electrolyte for the lithium ion battery of any one of the above-mentioned.
The benzotriazole phosphate compound with the structure can be used as a phagocytic agent of Hydrogen Fluoride (HF) in a battery system on one hand, and on the other hand, the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, and can be coordinated with high-valence transition metal nickel, manganese, iron and the like in situ, so that transition metal nickel, manganese and iron ions are inhibited from dissolving out, the problem that the electrolyte is oxidized and decomposed to generate gas is solved, the problem that the battery generates gas in the high-voltage charge and discharge process is solved, the cycle performance of the battery in the high-voltage charge and discharge process is improved, the service life of the battery is prolonged, and the safety performance of the battery is improved. Furthermore, the phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and on the other hand, when lithium salt of electrolyte comprises lithium hexafluorophosphate, the phosphoramide framework can be prepared by combining with hexafluorophosphate ionsTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery. Further, the additive has lower oxidation potential, a compact and stable passivation film can be formed on the surface of the positive electrode in the first charging process, the oxidative decomposition of the organic solvent of the electrolyte on the surface of the positive electrode can be effectively inhibited, and the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process is effectively solved.
In some embodiments of the present application, the lithium ion battery is a ternary lithium ion battery, that is, a lithium battery using a ternary positive electrode material of nickel cobalt lithium manganate (Li (nicoman) O 2) or nickel cobalt lithium aluminate as a positive electrode material, especially for a ternary lithium ion battery using a ternary system of high nickel and medium nickel and high voltage, the problems of electrolyte consumption, gas production and battery structure damage caused by the reaction of the electrolyte due to easy dissolution of transition metal ions in the high voltage charging and discharging process of the battery are effectively solved, the cycle performance of the battery in the high voltage charging and discharging process is significantly improved, the service life of the battery is prolonged, and the safety performance of the battery is improved.
The advantageous effects that can be achieved by the present application will be further described below with reference to examples and comparative examples.
Example 1
Relates to electrolyte for a lithium ion battery, the lithium ion battery and a preparation method thereof, wherein the method comprises the following steps:
In a glove box filled with argon (moisture <10ppm, oxygen content <1 ppm), ethylene Carbonate (EC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) were mixed at 30:60:10, adding 1.1mol/L lithium hexafluorophosphate (LiPF 6) into the mixed solution, dissolving, adding 0.2% of benzotriazole phosphate compound B1, 1% of Vinylene Carbonate (VC), 1% of ethylene sulfate (DTD) and 0.5% of lithium difluorophosphate (LiPO 2F2) into the mixed solution, and stirring to obtain the electrolyte for the lithium ion battery.
And (3) injecting the prepared electrolyte for the lithium ion battery into a fully dried 4.35V NCM 811/graphite soft package battery, and carrying out the working procedures of placing at 45 ℃, high-temperature clamp formation, secondary sealing and the like, thereby carrying out battery performance test.
Example 2
The difference from example 1 is that the benzotriazole-based phosphate compound B1 was replaced with the same addition amount of the benzotriazole-based phosphate compound B2.
Example 3
The difference from example 1 is that the benzotriazole-based phosphate compound B1 was replaced with the same addition amount of the benzotriazole-based phosphate compound B3.
Example 4
The difference from example 1 is that the addition amount of the benzotriazole-based phosphate ester compound B1 is 0.5 wt% of the total mass of the electrolyte.
Example 5
The difference from example 1 is that 0.5 wt% by mass of the total electrolyte solution of the benzotriazole-based phosphate ester compound B2 was used instead of 0.2. 0.2 wt% by mass of the total electrolyte solution of the benzotriazole-based phosphate ester compound B1.
Example 6
The difference from example 1 is that benzotriazole-based phosphate compound B1 was replaced with benzotriazole-based phosphate compound B3 in an amount of 0.5 wt% by weight of the total electrolyte, and benzotriazole-based phosphate compound B1 in an amount of 0.2: 0.2 wt% by weight of the total electrolyte.
Example 7
The difference from example 1 is that the addition amount of the benzotriazole-based phosphate ester compound B1 is 1wt% of the total mass of the electrolyte.
Example 8
The difference from example 1 is that benzotriazole-based phosphate compound B1 was replaced with benzotriazole-based phosphate compound B2 in an amount of 1wt% by weight of the total electrolyte, and benzotriazole-based phosphate compound B1 in an amount of 0.2: 0.2 wt% by weight of the total electrolyte.
Example 9
The difference from example 1 is that benzotriazole-based phosphate compound B1 was replaced with benzotriazole-based phosphate compound B3 in an amount of 1wt% by weight of the total electrolyte, and benzotriazole-based phosphate compound B1 in an amount of 0.2: 0.2 wt% by weight of the total electrolyte.
Example 10
The difference from example 1 is that the addition amount of the benzotriazole-based phosphate ester compound B1 is 0.05 wt% of the total mass of the electrolyte.
Example 11
The difference from example 1 is that the addition amount of the benzotriazole-based phosphate ester compound B1 is 2wt% of the total mass of the electrolyte.
Example 12
The difference from example 1 is that a lithium salt combination of LiPF 6 +0.3mol/L LiFSI of 0.8mol/L was used.
Example 13
The difference from example 1 is that the lithium salt is LiFSI of 1.1 mol/L.
Example 14
The difference from example 1 is that the prepared electrolyte for lithium ion battery was injected into a fully dried 3.65V lithium iron phosphate/graphite soft pack battery, and after the processes of standing at 45 ℃, high temperature clamp formation, secondary sealing, etc., battery performance test was performed.
Example 15
The difference from example 1 is that the benzotriazole-based phosphate ester compound has the following structure:
(denoted as B4)
Example 16
The difference from example 1 is that the benzotriazole-based phosphate ester compound has the following structure:
(denoted as B5)
Comparative example 1
The difference from example 1 is that a benzotriazole-based phosphate compound was not added to the electrolyte for a lithium ion battery.
Comparative example 2
The difference from example 1 is that the benzotriazole-based phosphate ester compound B1 is replaced with tris (trimethylsilane) phosphite and benzotriazole in a molar ratio of 1:1, and the addition amount is 0.5% of the mass of the electrolyte.
Comparative example 3
The difference from example 1 is that the benzotriazole-based phosphate compound B1 was replaced with tris (trimethylsilane) phosphate and benzotriazole in a molar ratio of 1:1, and the addition amount was 0.5% by mass of the electrolyte.
Lithium ion battery performance test
1. Normal temperature cycle performance
And (3) under the condition of normal temperature (25 ℃), charging the lithium ion battery to 4.35V at a constant current and constant voltage of 0.5C, and discharging the lithium ion battery to 2.8V at a constant current of 1.0C. After 2500 cycles of charge and discharge, the capacity retention after 2500 th cycle was calculated.
2. High temperature cycle performance
And (3) under the condition of high temperature (45 ℃), charging the constant current and the constant voltage of 0.5C of the lithium ion battery to 4.35V, and then discharging the constant current of 1.0C to 2.8V. After 2500 cycles of charge and discharge, the capacity retention after 2500 th cycle was calculated.
3. Low temperature cycle performance
And (3) under the condition of low temperature (-10 ℃), charging the constant current and the constant voltage of 0.5C of the lithium ion battery to 4.35V, and then discharging the constant current of 1.0C to 2.8V. After 500 cycles of charge and discharge, the capacity retention after 500 th cycle was calculated.
4. High temperature storage performance
And (3) under the condition of normal temperature (25 ℃), charging the lithium ion battery to 4.35V at a constant current and constant voltage of 0.5C, and then placing the lithium ion battery in a high-temperature box at 55 ℃ for standing for 90 days to test the thickness increase rate of the battery after storage.
The results of the above tests are listed in table 1.
TABLE 1
According to the above examples and comparative examples, the electrolyte for lithium ion batteries prepared by the present invention has significantly improved cycle performance and significantly reduced gas production rate during high voltage charge and discharge due to the inclusion of the benzotriazole-based phosphate compound having the structure of formula I.
From examples 1 to 11, it can be seen that the high-low temperature cycle performance of the battery is closely related to the addition amount of the benzotriazole-based phosphate ester compound, and when the addition amount of the benzotriazole-based phosphate ester compound is 0.2% -1% of the total mass of the electrolyte, the prepared lithium battery has good high temperature cycle performance. However, when the addition amount of the benzotriazole-based phosphate compound is further increased to 2% of the total mass of the electrolyte as in example 11, the high-temperature cycle performance of the prepared lithium battery is rather reduced, which may be because the benzotriazole-based phosphate compound is not completely reacted with the positive and negative interfaces in the early stage and the impedance is continuously increased due to the continuous action of the benzotriazole-based phosphate additive with the positive interface active potential in the high SOC state during the late cycle when the addition amount of the benzotriazole-based phosphate compound is excessive, and the benzotriazole-based phosphate additive which is not fully reacted exists in the electrolyte in a free state and has thermodynamic instability under the catalysis of acidity and heat, thereby affecting the cycle performance of the battery; when the addition amount of the benzotriazole-based phosphate compound is too low, for example, 0.05% of the total mass of the electrolyte, film formation at the positive and negative electrode interfaces is impossible, and the improvement of the battery performance is limited. Therefore, the benzotriazole-based phosphate compound with the structure of formula I is preferably 0.1-2 wt% of the mass of the electrolyte for the lithium ion battery, and is particularly favorable for improving the performance of the battery when the addition amount of the benzotriazole-based phosphate compound is 0.2-1 wt%.
It can be seen from examples 12 to 13 that the electrolyte additive for lithium batteries of the present application, which replaces the type of lithium salt within the scope of the present application, has excellent battery performance. From example 14, it can be seen that the cycle performance and storage safety performance of the battery can be better exerted when the same electrolyte formulation is used for injecting the lithium iron phosphate/graphite soft-pack battery, which shows that the electrolyte formulation is also applicable to a non-ternary system.
Comparative example 1 compared with example 1, the electrolyte for lithium battery was not added with benzotriazole-based phosphate compound, the cycle performance of the soft pack battery was significantly reduced, the thickness of the battery after high temperature storage was significantly increased, and gas was generated.
The cycle performance of the soft pack battery of comparative examples 2 and 3 is significantly reduced compared with that of example 1, and particularly the low temperature cycle performance is significantly deteriorated, probably due to the fact that the impedance of the battery is significantly increased by introducing tris (trimethylsilyl) phosphite or tris (trimethylsilyl) phosphate and benzotriazole in a molar ratio of 1:1, and the polarization is increased during the cycle of the battery, so that the heat loss of the battery itself is increased, and the discharge of a sufficiently large current is not possible. In addition, the increase of the impedance causes the reduction of the battery discharge operating voltage, shortens the discharge time, and has serious influence on the battery performance, the service life and the like. In addition, the thickness of the batteries of comparative examples 2 and 3 was also significantly increased, and a significant swelling phenomenon was generated, and gas was generated, indicating that when an additive of tris (trimethylsilane) phosphite or a combination of tris (trimethylsilane) phosphate and benzotriazole was used, it was not possible to suppress the high-valence transition metal ions which were continuously eluted from the positive electrode at a high voltage, thereby reducing oxidative decomposition of the electrolyte, suppressing gas generation of the soft-packed battery, and thus improving the safety performance of the battery.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the benzotriazole phosphate compound serving as the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, so that the in-situ coordination can be carried out on the byproducts and high-valence transition metal nickel, manganese, iron and the like, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, so that the problem that the electrolyte is oxidized and decomposed to generate gas is avoided, the problem that the battery generates gas in the high-voltage charge and discharge process is effectively solved, the cycle performance of the battery in the high-voltage charge and discharge process is improved, the service life of the battery is prolonged, and the safety performance of the battery is improved. Furthermore, the phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and on the other hand, when lithium salt of electrolyte comprises lithium hexafluorophosphate, the phosphoramide framework can be prepared by combining with hexafluorophosphate ionsTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery. Further, the additive has lower oxidation potential, a compact and stable passivation film can be formed on the surface of the positive electrode in the first charging process, the oxidative decomposition of the organic solvent of the electrolyte on the surface of the positive electrode can be effectively inhibited, and the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process is effectively solved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent substitution, and discharge of a large current compared to example 1 of examples 2 and 3 are all within the spirit and principles of the present invention. In addition, the increase of the impedance causes the reduction of the battery discharge operating voltage, shortens the discharge time, and has serious influence on the battery performance, the service life and the like. The batteries of comparative examples 2 and 3 also had significantly increased thickness and had significantly increased swelling to generate gas, indicating that the use of the additive of tris (trimethylsilyl) phosphite or a combination of tris (trimethylsilyl) phosphate and benzotriazole did not suppress the dissolution of the high-valence transition metal ions from the positive electrode at high voltage, thereby reducing oxidative decomposition of the electrolyte, suppressing gassing of the soft-pack battery and improving the safety performance of the battery.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the benzotriazole phosphate compound serving as the additive can be used as a phagocytic agent of water and Hydrogen Fluoride (HF) in a battery system, and the molecular structure of byproducts generated after the phagocytic agent is provided with P, O, N and other heteroatoms, so that the in-situ coordination can be carried out on the byproducts and high-valence transition metal nickel, manganese, iron and the like, and the dissolution of transition metal nickel, manganese and iron ions is inhibited, so that the problem that the electrolyte is oxidized and decomposed to generate gas is avoided, the problem that the battery generates gas in the high-voltage charge and discharge process is effectively solved, the cycle performance of the battery in the high-voltage charge and discharge process is improved, the service life of the battery is prolonged, and the safety performance of the battery is improved. Furthermore, the phosphoramide framework is beneficial to uniform growth of Cathode Electrolyte Interface (CEI) and anode solid electrolyte phase interface (SEI) films on one hand, greatly improves migration quantity of lithium ions, and on the other hand, when lithium salt of electrolyte comprises lithium hexafluorophosphate, the phosphoramide framework can be prepared by combining with hexafluorophosphate ionsTo inhibit the generation of harmful substances, thereby providing guarantee for the long cycle life and high safety of the medium-nickel high-voltage/high-nickel battery. Further, the additive has lower oxidation potential, a compact and stable passivation film can be formed on the surface of the positive electrode in the first charging process, the oxidative decomposition of the organic solvent of the electrolyte on the surface of the positive electrode can be effectively inhibited, and the problem of rapid capacity decay of the battery in the high-voltage charging and discharging process is effectively solved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. An electrolyte additive is characterized by comprising a benzotriazole phosphate compound with a structure shown in a formula I,
I is a kind of
In the formula I, R 1 and R 2 are respectively and independently selected from any one of a first substituent and a second substituent, and R 3 and R 4 are respectively and independently selected from any one of a hydrogen atom, the first substituent and the second substituent;
The first substituent is a halogen atom, a cyano group, a carboxylic acid ester group containing 1-6 carbon atoms, an ether group containing 1-6 carbon atoms or an aryl group containing 6-18 carbon atoms; the second substituent is a substituted or unsubstituted straight-chain alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted straight-chain alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted unsaturated hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms, or a substituted or unsubstituted silane group having 1 to 6 carbon atoms, and when substituted, the substituent is the first substituent;
the electrolyte additive is applied to a lithium ion battery with positive electrode materials comprising any one or more elements of nickel, manganese and iron.
2. The electrolyte additive according to claim 1, wherein R 1 and R 2 are each independently selected from any one of the second substituents, and R 1 and R 2 are the same;
And/or, each of R 3 and R 4 is independently selected from any one of a hydrogen atom and the first substituent, and R 3 and R 4 are the same.
3. The electrolyte additive according to claim 1, wherein the second substituent is any one of a linear alkyl group having 2 to 3 carbon atoms, a linear alkoxy group having 2 to 3 carbon atoms, and a silane group having 3 to 6 carbon atoms.
4. The electrolyte additive according to claim 1, wherein the first substituent is any one of a halogen atom and a cyano group.
5. The electrolyte additive of any one of claims 1 to 4 further comprising a negative film-forming additive comprising any one or more of fluoroethylene carbonate, vinylene carbonate, ethylene sulfate, propylene sulfate, 4-methyl ethylene sulfate, vinyl ethylene carbonate, 4-ethyl ethylene sulfate, 1, 3-propane sultone, vinyl sulfite, tri (trimethylsilyl) borate, and triallyl isocyanurate.
6. An electrolyte for a lithium ion battery, characterized in that the electrolyte for a lithium ion battery comprises: the electrolyte additive comprises lithium salt, an organic solvent and an additive, wherein the additive is the electrolyte additive according to any one of claims 1 to 5, and the benzotriazole-based phosphate ester compound with the structure shown in formula I in the electrolyte additive accounts for 0.2% -1% of the mass of the electrolyte for the lithium ion battery.
7. The electrolyte for lithium ion batteries according to claim 6, wherein the additive accounts for 0.2-5 wt% of the mass of the electrolyte for lithium ion batteries.
8. The electrolyte for a lithium ion battery according to claim 6, wherein the lithium salt comprises any one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorobisoxalato phosphate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, lithium difluorophosphate, lithium tetrafluorophosphate, potassium bisfluorosulfonyl imide, 4, 5-dicyano-2-trifluoromethyl-imidazole lithium, lithium methylsulfate, lithium ethylsulfate, and lithium bis (nonafluorobutylsulfonyl) imide;
And/or the organic solvent comprises any one or more of chain carbonate and cyclic carbonate; the chain carbonic ester is selected from any one or more of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and dipropyl carbonate; the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate.
9. A lithium ion battery, comprising: positive electrode sheet, negative electrode sheet, separator and electrolyte, characterized in that the electrolyte is the electrolyte for a lithium ion battery according to any one of claims 6 to 8.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010092897A1 (en) * | 2009-02-16 | 2010-08-19 | コニカミノルタホールディングス株式会社 | Electrolyte composition, and secondary battery |
| CN105070953A (en) * | 2015-09-16 | 2015-11-18 | 高金刚 | Environment-friendly storage battery electrolyte and preparation method thereof |
| CN107210481A (en) * | 2014-09-19 | 2017-09-26 | 索尔维公司 | Non-aqueous electrolyte composition |
| CN109273764A (en) * | 2018-09-14 | 2019-01-25 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| CN110752406A (en) * | 2019-10-28 | 2020-02-04 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
| CN111916826A (en) * | 2020-07-22 | 2020-11-10 | 梅州市量能新能源科技有限公司 | Electrolyte and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN112216862A (en) * | 2019-07-11 | 2021-01-12 | 杉杉新材料（衢州）有限公司 | High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery |
| JP2021009755A (en) * | 2019-06-28 | 2021-01-28 | 旭化成株式会社 | Nonaqueous electrolyte and nonaqueous secondary battery |
| CN112640180A (en) * | 2019-06-28 | 2021-04-09 | 旭化成株式会社 | Nonaqueous electrolyte solution and nonaqueous secondary battery |
| CN113921906A (en) * | 2021-09-27 | 2022-01-11 | 湖南法恩莱特新能源科技有限公司 | High-voltage electrolyte additive, high-voltage electrolyte and lithium ion battery |
| CN114287077A (en) * | 2020-05-29 | 2022-04-05 | 旭化成株式会社 | Nonaqueous electrolyte solution, battery pack, and method for producing battery pack |
| CN115275340A (en) * | 2022-08-09 | 2022-11-01 | 湖南法恩莱特新能源科技有限公司 | High-voltage electrolyte and preparation method and application thereof |
| EP4175003A1 (en) * | 2020-06-26 | 2023-05-03 | Soulbrain Co., Ltd. | Electrolyte additive, battery electrolyte comprising same, and secondary battery comprising same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7638243B2 (en) * | 2006-03-22 | 2009-12-29 | Novolyte Technologies Inc. | Stabilized nonaqueous electrolytes for rechargeable batteries |
| WO2019018413A1 (en) * | 2017-07-17 | 2019-01-24 | NOHMs Technologies, Inc. | Modified ionic liquids containing triazine |
-
2024
- 2024-01-24 CN CN202410098523.8A patent/CN117613389B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010092897A1 (en) * | 2009-02-16 | 2010-08-19 | コニカミノルタホールディングス株式会社 | Electrolyte composition, and secondary battery |
| CN107210481A (en) * | 2014-09-19 | 2017-09-26 | 索尔维公司 | Non-aqueous electrolyte composition |
| CN105070953A (en) * | 2015-09-16 | 2015-11-18 | 高金刚 | Environment-friendly storage battery electrolyte and preparation method thereof |
| CN109273764A (en) * | 2018-09-14 | 2019-01-25 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| CN112640180A (en) * | 2019-06-28 | 2021-04-09 | 旭化成株式会社 | Nonaqueous electrolyte solution and nonaqueous secondary battery |
| JP2021009755A (en) * | 2019-06-28 | 2021-01-28 | 旭化成株式会社 | Nonaqueous electrolyte and nonaqueous secondary battery |
| CN112216862A (en) * | 2019-07-11 | 2021-01-12 | 杉杉新材料（衢州）有限公司 | High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery |
| CN110752406A (en) * | 2019-10-28 | 2020-02-04 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
| CN114287077A (en) * | 2020-05-29 | 2022-04-05 | 旭化成株式会社 | Nonaqueous electrolyte solution, battery pack, and method for producing battery pack |
| EP4175003A1 (en) * | 2020-06-26 | 2023-05-03 | Soulbrain Co., Ltd. | Electrolyte additive, battery electrolyte comprising same, and secondary battery comprising same |
| CN111916826A (en) * | 2020-07-22 | 2020-11-10 | 梅州市量能新能源科技有限公司 | Electrolyte and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN113921906A (en) * | 2021-09-27 | 2022-01-11 | 湖南法恩莱特新能源科技有限公司 | High-voltage electrolyte additive, high-voltage electrolyte and lithium ion battery |
| CN115275340A (en) * | 2022-08-09 | 2022-11-01 | 湖南法恩莱特新能源科技有限公司 | High-voltage electrolyte and preparation method and application thereof |
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