CN116979144A - Electrolyte additive, electrolyte and lithium ion battery - Google Patents
Electrolyte additive, electrolyte and lithium ion battery Download PDFInfo
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- CN116979144A CN116979144A CN202210427095.XA CN202210427095A CN116979144A CN 116979144 A CN116979144 A CN 116979144A CN 202210427095 A CN202210427095 A CN 202210427095A CN 116979144 A CN116979144 A CN 116979144A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 87
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 52
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 26
- -1 cyano, siloxy, amino, phenyl Chemical group 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 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 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 2
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 13
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000013375 chromatographic separation Methods 0.000 description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 2
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000993376 Homo sapiens Hypermethylated in cancer 2 protein Proteins 0.000 description 1
- 102100031613 Hypermethylated in cancer 2 protein Human genes 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to the field of lithium ion battery electrolyte, and discloses an electrolyte additive, electrolyte and a lithium ion battery, wherein the structural general formula of the additive is shown as the following formula (1),
Description
Technical Field
The application relates to the field of lithium ion battery electrolyte, in particular to an electrolyte additive, electrolyte and a lithium ion battery.
Background
With the application of lithium ion batteries in the field of electric automobiles, the industry is pursuing higher energy density of lithium batteries, which is also an important index reflecting battery technology. For this reason, positive and negative electrode materials with higher gram capacity are required, and as the current commercial choice in the power battery industry, a high nickel ternary material is generally used for the positive electrode, and a silicon-based material is used for the negative electrode. However, the high nickel material has strong oxidizing property to the electrolyte after delithiation, resulting in gas production, metal element dissolution and capacity fading of the battery. And the silicon-based material has huge volume shrinkage in the process of lithium intercalation, so that SEI films on the surface of the silicon-based material are easy to crack, repeated growth of the SEI films occurs, and finally a series of safety problems such as increased battery impedance, gas expansion, capacity attenuation and the like and performance attenuation are caused.
In a ternary material power battery, electrolyte selection is also an important aspect affecting battery performance. At present, two most commonly used electrolyte additives are Vinylene Carbonate (VC) and Propylene Sulfite (PS), which can remarkably improve the high-temperature storage performance and the cycle performance of the battery, but have the biggest defects of remarkably increasing the impedance and reducing the multiplying power and the low-temperature performance. In the prior art, aiming at the electrolyte additive of the high-nickel system lithium battery, the problem of overlarge impedance caused by too high film forming rate is often existed, and the high-temperature storage performance is improved, and meanwhile, the rate charging performance and the low-temperature performance of the battery are greatly influenced. Therefore, development of electrolyte additives which can form a good SEI film on the surface of a negative electrode, improve the interface stability of materials and avoid high-temperature gas expansion and overlarge impedance of a battery is important.
Disclosure of Invention
The application aims to solve the problems that in the prior art, the film forming rate of an electrolyte additive is too high, so that impedance is too high, and a formed battery is difficult to have both high-temperature storage performance and multiplying power and low-temperature performance.
In order to achieve the above object, a first aspect of the present application provides an electrolyte additive, wherein the structural general formula of the additive is shown as formula 1 below,
wherein X, Y, Z contains at least one unsaturated group.
In a second aspect, the present application provides an electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises a first additive, and the first additive is the electrolyte additive provided in the first aspect.
The third aspect of the application provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte is the electrolyte provided in the second aspect.
Through the technical scheme, the beneficial technical effects obtained by the application are as follows:
the electrolyte additive provided by the application can form a stable elastic SEI film on the anode and the cathode, protect the anode interface and improve the interface stability of the anode surface.
The electrolyte containing the additive can improve the high-temperature circulation, high-temperature storage, rate charging performance and low-temperature discharging performance of the lithium ion battery, and effectively inhibit lithium precipitation of the battery.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present application, the term "SEI" is abbreviated as "solid electrolyte interphase" and refers to a passivation layer formed by reacting an electrode material with an electrolyte at a solid-liquid phase interface and covering the surface of the electrode material in the first charge and discharge process of a liquid lithium ion battery.
The first aspect of the application provides an electrolyte additive, which is characterized in that the structural general formula of the additive is shown as the following formula 1,
wherein X, Y, Z contains at least one unsaturated group.
The additive of the application contains a plurality of N atoms with stronger electronegativity, can reduce the LUMO energy of the whole additive molecule and is easier to be reduced to form a fast lithium ion conductor Li 3 N, ion conductivity sigma of 6X 10 -3 S cm -1 And is more beneficial to ion transmission of ions in the SEI film.
According to a preferred embodiment of the present application, the unsaturated group comprises at least one of alkenyl, alkynyl, halogen, cyano, siloxy, amino, phenyl, nitro, phosphate and phosphite.
According to a preferred embodiment of the present application, each of the formulae 1 and X, Y, Z is independently selected fromAt least one of hydrogen, halogen, cyano, siloxy, amino, phenyl, nitro, phosphate, phosphite, and at least one of X, Y, Z is ∈ ->Wherein R is 1 、R 2 Each independently selected from at least one of hydrogen, halogen, cyano, siloxy, amino, phenyl, nitro, phosphate, phosphite; m and n are positive integers, and the values of m and n satisfy the following conditions: m is more than or equal to 1 and less than or equal to 3, n is more than or equal to 1 and less than or equal to 3.
By substituent modification through carbon-carbon double or triple bonds in the above-mentioned unsaturated groups, e.g. electron-withdrawing groups-F, -NH 2 、-NO 2 And the oxidation polymerization voltage and the polymerization reaction rate of double bonds can be regulated and controlled, so that the film forming impedance of an anode of the additive is reduced, meanwhile, substances containing carbon-carbon double bonds or triple bonds are used as the additive to easily perform electrochemical polymerization reaction on the surface of an electrode to form a film, the formed SEI film has good elasticity, and the SEI film cannot be broken in the process of removing lithium from the material, so that the SEI film cannot be repeatedly grown, and the cycle performance of the electrode material is remarkably improved. For example, in high nickel lithium ion systemsWhen the high-nickel anode is used in a battery, the interface stability of the high-nickel anode surface can be improved, the reduction of solvent molecules on the anode surface and the oxidation of the anode surface are prevented, and the high-temperature cycle and storage performance of the battery are obviously improved.
According to the present application, any additive satisfying the aforementioned requirements may be used in the present application, and there is no particular requirement for the specific kind of the additive, preferably the additive is selected from 1- (4-amino-but-2-enyl) -3, 5-difluoro- [1,3,5] triazine-2, 4, 6-trione (structure shown as formula 2, denoted as PUHIC-1), 1- (4-amino-but-2-ynyl) -3, 5-di-prop-2-ynyl- [1,3,5] triazine-2, 4, 6-trione (structure shown as formula 3, denoted as PUHIC-2), 1, 3-diallyl-5- (3-phenyl-allyl) - [1,3,5] triazine-2, 4, 6-trione (structure shown as formula 4, denoted as HIC-3), 1- (3-phenyl-prop-2-ynyl) -3, 5-di-prop-2-ynyl- [1,3,5] triazine-2, 4, 6-trione (structure shown as formula 3,5] triazine-2, 4, 6-trione (structure shown as formula 4, denoted as formula 4), 1- (3-phenyl-prop-2-alkynyl) -3, 5-di-prop-2-alkynyl) -2, 6-trione (structure shown as formula 4, denoted as formula 4, 3,5] tri-2-n-2 1, 3-diallyl-5- [4- (allyl-dimethyl-silanyl) -but-2-ynyl ] - [1,3,5] triazin-2, 4, 6-trione (structure shown as formula 7, denoted as PUHIC-6), dimethyl [4- (3, 5-diallyl-2, 4, 6-trioxo- [1,3,5] triazin-1-yl) -but-2-ynyl ] -phosphonate (structure shown as formula 8, denoted as PUHIC-7), dimethyl 5- (3, 5-diallyl-2, 4, 6-trioxo- [1,3,5] triazin-1-yl) -pent-3-enyl ester of phosphoric acid (structure shown as formula 9, denoted as PUHIC-8), 5- { 3-allyl-5- [4- (allyl-dimethyl-silanyl) -but-2-ynyl ] -2,4, 6-trioxo- [1,3,5] triazin-1-yl } -pent-3-enyl ester (structure shown as formula 10, denoted as formula 9),
according to a preferred embodiment of the present application, the method for preparing the additive comprises: in an organic solvent, an isocyanurate compound and a halogenated compound are mixed and heated for reaction to synthesize the electrolyte additive shown in the formula 1, and the reaction principle is shown in the formula 11.
Wherein the isocyanurate compound has the structure ofThe halogenated compound depends on the specific kind of X, Y, Z in the general structural formula shown in formula 1. For example, when the isocyanurate compound is introduced into the X substitution site, the corresponding halogenated compound is AX, wherein A represents a halogen element, which may be selected from Cl, br or I element, preferably Br element. When X, Y, Z in the structural general formula shown in the formula 1 is the same substituent group, providing a halogenated compound corresponding to the substituent group; when X, Y, Z in the structural general formula shown in formula 1 is two or three different substituent groups, the provided halogenated compound comprises two or three halogenated compounds corresponding to the different substituent groups respectively. It will be appreciated by those skilled in the art that different target products can be synthesized accordingly by varying the R groups of the halogenated compounds.
Preferably, the organic solvent may be selected from any organic solvents that are capable of sufficiently dissolving and dispersing the isocyanurate compound and the halogenated compound and do not participate in the reaction under heating, and for example, may be selected from N, N-Dimethylformamide (DMF).
Further, after the reaction is finished, the target product is separated and collected. Preferably, the target product may be separated by a chromatographic separation column.
For example, the preparation method of the additive comprises the following steps: 0.02mol of isocyanurate compound 1 and 0.06mol of bromo compound 2 were dissolved in 80mL of DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. The target product 3 was separated by a chromatographic column. The synthetic reaction equation is shown in formula 12:
in a second aspect, the present application provides an electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises a first additive, and the first additive is the electrolyte additive provided in the first aspect.
The first additive can be used as the only additive of the electrolyte, and can also be matched with other additives for use. According to a preferred embodiment of the application, the electrolyte further comprises a second additive selected from the group consisting of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), 1-propylene-1, 3-sultone (PES), ethylene carbonate (VEC), tris (trimethylsilane) phosphite (TMSPi), tris (trimethylsilane) phosphate (TMSP), tris (trimethylsilane) borate (TMSB), lithium difluorosulfonimide (LiFSI), lithium difluorophosphate (LiPO) 2 F 2 ) At least one of lithium difluorooxalato borate (LiODFB), lithium difluorooxalato phosphate (LiODFP), lithium bisoxalato borate (LiBOB), and Methylene Methane Disulfonate (MMDS). In this preferred manner, the first additive and the second additive can be synergistically formed into a film, e.g., liFSI, liPO is added 2 F 2 Inorganic additives such as lithium difluoroborate (LiODFB) can supplement film forming components, so that the compactness and the integrity of the SEI film are improved, and better performance of the battery is realized.
According to a preferred embodiment of the application, the lithium salt is selected from LiPF 6 One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI); further preferred is LiPF 6 。
According to a preferred embodiment of the present application, the organic solvent is at least one selected from the group consisting of Ethylene Carbonate (EC), propylene Carbonate (PC), propylene carbonate (EMC), propylene carbonate (DEC); preferably, the organic solvent may be a combination of EC and EMC, or a combination of EC, PC, EMC and EC, DEC, EMC; further preferred is a combination of EC, PC, EMC and DEC. In the above preferred case, it is advantageous to achieve the minimum viscosity and the maximum ionic conductivity of the electrolyte.
According to a preferred embodiment of the present application, the mass ratio of ethylene carbonate, propylene carbonate is (15-35): (0-15): (10-80): (0-30), more preferably (13-33): (2-14): (11-78): (2-28).
According to a preferred embodiment of the application, the first additive is present in an amount of 0.02 to 3wt%, preferably 0.1 to 1wt%, based on 100% of the total mass of the electrolyte; too low a concentration of the additive may result in insufficient film formation, while too high a concentration may result in excessive film formation resistance to affect the cycle performance of the battery.
According to a preferred embodiment of the application, the second additive is present in an amount of 0-10wt%, preferably 0.3-6wt%; the lithium salt content is 11-14wt%, preferably 12-13wt%.
A third aspect of the present application provides a lithium ion battery, including a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is the electrolyte provided in the second aspect.
In the application, the anode and cathode materials of the lithium ion battery are not strictly limited, and any commonly used anode and cathode materials can be selected, for example, the anode materials can be nickel cobalt lithium manganate anode materials or lithium cobaltate anode materials, and the cathode materials can be at least one of silicon materials, carbon materials or silicon-carbon composite materials. Preferably, the active material of the positive electrode is a ternary positive electrode material or a high nickel positive electrode material, wherein the high nickel positive electrode material refers to a ternary positive electrode material containing nickel, and the molar percentage of nickel ions in the total amount of other metal ions except lithium ions is calculated, and the ternary positive electrode material contains, but is not limited to, ni83, ni50, ni60, ni70, ni80, ni88, ni90 and other positive electrode materials, wherein Ni83 refers to a ternary positive electrode material containing nickel, and the content of nickel ions in the total amount of other metal ions except lithium ions in the positive electrode active material is 83 mol%. Preferably, the negative electrode material may be at least one of carbon-coated silicon, silicon oxide, silicon-carbon mixture, or graphite. The electrolyte containing the first additive can form a good SEI film on the surface of the negative electrode, improve the interface stability of a high-nickel material, prevent reduction of solvent molecules on the surface of the negative electrode and oxidation of the surface of the positive electrode, improve the problem of poor cycle performance of a silicon-based material, and improve the high-temperature cycle and storage performance of a battery.
The following examples illustrate the advantages of the present application in detail, but are not limited to the scope of the application.
The starting materials in the examples below were all from commercial sources.
Preparation example 1
Mixing 0.02mol of isocyanurate compound and 0.02mol of isocyanurate compoundBr, 0.04mol HF were dissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-1, by a chromatographic separation column, wherein the structure is shown in a formula 2.
Preparation example 2
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02molDissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-2, by a chromatographic separation column, wherein the structure is shown in a formula 3.
Preparation example 3
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02mol/>Dissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-3, by a chromatographic separation column, wherein the structure is shown in a formula 4.
Preparation example 4
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02mol/>Dissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-4, by a chromatographic separation column, wherein the structure is shown in a formula 5.
Preparation example 5
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02molDissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-5, by a chromatographic separation column, wherein the structure is shown in a formula 6.
Preparation example 6
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02molDissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-6, by a chromatographic separation column, wherein the structure is shown in formula 7.
Preparation example 7
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02molDissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. By chromatographic separation columnsThe target product, namely PUHIC-7, is separated, and the structure is shown as a formula 8.
Preparation example 8
Mixing 0.02mol of isocyanurate compound and 0.04mol of isocyanurate compoundBr、0.02molDissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-8, by a chromatographic separation column, wherein the structure is shown in a formula 9.
Preparation example 9
Mixing 0.02mol of isocyanurate compound and 0.02mol of isocyanurate compoundBr、0.02mol0.02mol/>Br was dissolved in 80mL DMF. The reaction flask was warmed from room temperature to 125℃and kept at constant temperature for 6h. Separating the target product, namely PUHIC-9, by a chromatographic separation column, wherein the structure is shown in a formula 10.
Example 1
(1) Electrolyte preparation: 300g of EC,500g of EMC,200g of DEC are mixed in a glove box with a water content of less than 1ppm and an oxygen content of less than 2ppm, and an appropriate amount of fully dried LiPF is added 6 So that the lithium salt concentration of the electrolyte is 1mol/L, and the basic electrolyte is obtained. To the base electrolyte, 0.2% PUHIC-1 was added to obtain electrolyte E1.
(2) And (3) manufacturing a battery: positive electrode material Ni83, carbon black, conductive agent CNT, PVDF at 100:0.6:0.6:1.5, and then coated on an aluminum foil of 12 μm, and then dried at 85 ℃. Silicon coated silica, carbon black, SBR, CMC at 100:0.9:1.9:1.5 are uniformly mixed and coated on a copper foil of 8 mu m, and then dried at 90 ℃. The ceramic diaphragm is used as a diaphragm, and the positive and negative pole pieces are made into a battery in a winding or lamination mode, so that a dry battery core is obtained.
(3) The chemical composition and the volume-dividing process are as follows: and (3) sealing after injecting the liquid into the dry cell, and standing at 45 ℃ for 48 hours to fully infiltrate the electrolyte. The simulated battery was charged to 3.5V at 0.05C, 3.7V at 0.1C, 3.9V at 0.2C, and then aged at 45℃ for 48 h. After aging, the battery C1 is obtained by fully charging 0.33C and discharging 0.33C to 2.75V.
Example 2
The procedure of example 1 was followed, except that "0.2% PUHIC-2" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E2, and the resulting battery was C2.
Example 3
The procedure of example 1 was followed, except that "0.2% PUHIC-3" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E3, and the resulting battery was C3.
Example 4
The procedure of example 1 was followed, except that "0.2% PUHIC-4" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E4, and the resulting battery was C4.
Example 5
The procedure of example 1 was followed, except that "0.2% PUHIC-5" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E5, and the resulting battery was C5.
Example 6
The procedure of example 1 was followed, except that "0.2% PUHIC-6" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E6, and the resulting battery was C6.
Example 7
The procedure of example 1 was followed, except that "0.2% PUHIC-7" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E7, and the resulting battery was C7.
Example 8
The procedure of example 1 was followed, except that "0.2% PUHIC-8" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E8, and the resulting battery was C8.
Example 9
The procedure of example 1 was followed, except that "0.2% PUHIC-9" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E9, and the resulting battery was C9.
Example 10
The procedure of example 1 was followed, except that "0.2% PUHIC-1+1% LiPO2F2" was added to the electrolyte in place of "0.2% PUHIC-1", to obtain electrolyte E10, and the resulting battery was C10.
Example 11
The procedure described in example 1 was followed, except that "0.2% PUHIC-2+3% FEC+0.5% PST" was added to the electrolyte to "replace" 0.2% PUHIC-1", to obtain electrolyte E11, and the resulting battery was C11.
Example 12
The procedure of example 1 was followed, except that "0.2% PUHIC-3+1.5% LiFeSI" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E12, and the obtained cell was C12.
Example 13
The procedure of example 1 was followed, except that "0.2% PUHIC-4+1% PS" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E13, and the resulting battery was C13.
Example 14
According to the method described in example 1, except that the solvent ratio was "EC/EMC/dec=3/6/1" instead of "EC/EMC/dec=3/5/2", and "0.3% puhic-5+1% liodfp" instead of "0.2% puhic-1" was added to the electrolyte to obtain electrolyte E14, and the obtained battery was C14.
Example 15
According to the method described in example 1, except that the solvent was "EC/EMC/dec=3/6/1" instead of "EC/EMC/dec=3/5/2", and "0.3% puhic-6+1% libob" instead of "0.2% puhic-1" was added to the electrolyte to obtain electrolyte E15, and the obtained battery was C15.
Example 16
According to the method described in example 1, except that the solvent was "300g of EC and 700g of EMC" replace "300g of EC,500g of EMC,200g of DEC", and "0.3% PUHIC-7+0.3% of VC" replace "0.2% of PUHIC-1" was added to the electrolyte to obtain electrolyte E16, and the obtained battery was C16.
Example 17
According to the method described in example 1, except that the solvent was "300g of EC and 700g of EMC" replace "300g of EC,500g of EMC,200g of DEC", and "0.3% PUHIC-8+0.5% of VC" replace "0.2% PUHIC-1" was added to the electrolyte to obtain electrolyte E17, and the obtained battery was C17.
Example 18
According to the method described in example 1, except that the solvents were "250g of EC,50 g of PC, 600g of EMC and 100g of DEC" replace "300g of EC,500g of EMC,200g of DEC", and "0.5% PUHIC-9+3% FEC+1% DTD" replace "0.2% PUHIC-1" was added to the electrolyte to obtain electrolyte E18, and the resulting battery was C18.
Example 19
According to the method described in example 1, except that the solvents were "250g of EC,50 g of PC, 600g of EMC and 100g of DEC" replace "300g of EC,500g of EMC,200g of DEC", and "0.5% PUHIC-1+3% FEC+1% DTD+0.5% PS" replace "0.2% PUHIC-1" was added to the electrolyte to obtain electrolyte E19, and the resulting battery was C19.
Example 20
According to the method described in example 1, except that the solvents were "250g of EC,50 g of PC, 600g of EMC and 100g of DEC" replace "300g of EC,500g of EMC,200g of DEC", and "0.5% PUHIC-2+4% FEC+1% DTD+1% PS" replace "0.2% PUHIC-1" was added to the electrolyte to obtain electrolyte E20, and the resulting battery was C20.
Example 21
The procedure of example 1 was followed, except that "0.3% PUHIC-1" was added to the electrolyte instead of "0.2% PUHIC-1", to obtain electrolyte E21, and the resulting battery was C21.
Comparative example 1
The procedure of example 1 was followed, except that no additive was added to the electrolyte to obtain electrolyte DE1, and the obtained battery was DC1.
Comparative example 2
The procedure described in example 2 was followed, except that "0.01% PUHIC-2" was added to the electrolyte instead of "0.2% PUHIC-2", to obtain electrolyte DE2, and the resulting battery was DC2.
Comparative example 3
The procedure described in example 2 was followed, except that "5.1% PUHIC-2" was added to the electrolyte instead of "0.2% PUHIC-2", to obtain electrolyte DE3, and the resulting battery was DC3.
The compositions of the electrolytes E1 to E20 and DE1 to DE3 in examples 1 to 21 and comparative examples 1 to 3 according to the present application are shown in Table 1.
TABLE 1 electrolyte composition
/>
The lithium ion batteries C1-C21 and DC1-DC3 in examples 1-21 and comparative examples 1-3 of the present application were subjected to electrical performance tests as follows:
1. DCIR test
The cells of the examples and comparative examples (5 cells per condition, average of results) after the formation and the capacity division were charged at 25.+ -. 1 ℃ in an incubator at 0.5C CC for 30min, tested by HPPC method, discharged at 2C for 10s, and left to stand for 40s, and charged at 1.5C for 10s. The calculation method of the discharge DCR is dcr= (V) 0 -V 1 ) 2C (current). Wherein V is 0 At 2C pre-discharge voltage, V 1 Is the voltage after 2C discharge.
2. Normal temperature cycle test
The cells of the examples and comparative examples (5 cells per condition, average value of the results) after the formation and aging were charged to 4.2V at 0.5C CC-CV, the constant voltage was cut off at 0.05C current, the cells were left to stand for 30 minutes after charging, and the cells were left to stand for 30 minutes after discharging at 1℃ to 3V in an incubator at 25.+ -. 1 ℃ C. And the cycle was continued for 600 times. The capacity retention (%) is a percentage obtained by dividing the discharge capacity after 600 cycles by the first discharge capacity.
3. High temperature cycle test
The test temperature is 45+/-1 ℃ which is different from the normal temperature cyclic test.
4. High temperature storage test
The cells (5 cells per condition, and the average value thereof was obtained) after completion of the formation and aging capacity division in examples and comparative examples were charged to 4.2V at 0.5C CC-CV, and the constant voltage was kept at 0.05C current cut-off, and the charge capacity was recorded as C 0 . After storage at 55.+ -. 2 ℃ for 7 days and resting for 5 hours at room temperature, the cell was discharged to 2.75V at 1C, the discharge capacity was recorded as C 1 The capacity retention (%) =c was calculated 1 /C 0 *100%. Then charging to 4.2V with 0.5 CC-CV, and charging with 0.05C current cut-off, the charge capacity is marked as C 2 Then 1C is discharged to 2.75V, and the discharge capacity is marked as C 3 The capacity recovery rate (%) =c was calculated 3 /C 2 *100%. The cell expansion (%) was calculated by subtracting the thickness before storage from the thickness after storage, and dividing the obtained thickness difference by the percentage of the thickness before storage of the cell.
5. Low temperature discharge test
The cells (5 cells per condition, and the average value thereof was obtained) after the formation and aging capacity division in the examples and comparative examples were charged to 4.2V at 0.5C CC-CV, and the constant voltage was kept to 0.05C current cut-off and charged fully, and the charge capacity was recorded as C 0 . And then placing the mixture in a low-temperature cabinet at the temperature of-20+/-1 ℃ for 8 hours, and then carrying out discharge capacity test. Discharge rate was 0.5C, discharge cut-off voltage was 2.5V, discharge capacity was noted as C 1 . Then-20 ℃ discharge capacity retention (%) =c 1 /C 0 *100％。
6. Multiplying power charging test
The cells of the examples and comparative examples were charged to 4.2V at different rates of 0.33/0.5/1/1.5C CC-CV in an incubator at 25.+ -. 2 ℃ for 5 cells per condition (average value of the results)The current was cut off by pressing to 0.05C. The capacity charged at 0.33C is defined as Q 0 . Charge retention (%) =corresponding magnification Q X And (2) Q0 is 100%, so as to obtain the charge retention rate under different multiplying power.
7. Analysis of lithium analysis
The batteries after capacity division in examples and comparative examples (5 batteries per condition, the average value of the results was taken) were disassembled after 3 cycles of 1.5C charge and discharge, and whether or not lithium was eluted at the interface was observed.
The DCIR, cycle and storage test results of the lithium ion batteries C1-C21 and DC1-DC3 in examples 1-21 and comparative examples 1-3 of the present application are shown in Table 2, and the battery low temperature discharge, rate charge and lithium precipitation test results are shown in Table 3.
TABLE 2
TABLE 3 Low temperature discharge, rate charge and lithium analysis test results for batteries
From examples 1 to 4, 21 and comparative example 1, it can be seen from the results of table 2 that the additive PUHIC of the present application can form a stable elastic SEI film at the positive and negative electrodes, and can protect the negative electrode interface, thereby greatly improving the charge and cycle performance of the battery with less influence on the impedance of the battery.
As can be seen from example 2 and comparative example 2, the effect of the low additive concentration on the improvement of the battery performance is insufficient because the concentration is too low, the film formation is insufficient, and the too high additive concentration in comparative example 3 may cause the film formation resistance to be too large to affect the cycle performance of the battery.
Examples 5-20 illustrate that the additives of the present application may be combined with conventional additives to form a film through synergistic action, thereby improving the compactness and integrity of the SEI film and achieving superior performance of the battery.
From the results of table 3, it can be seen that the battery containing the additive of the present application in the electrolyte has significant improvements in low-temperature discharge performance, rate charge performance, and suppression of lithium precipitation.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the application, all falling within the scope of protection of the application.
Claims (10)
1. An electrolyte additive is characterized in that the structural general formula of the additive is shown as the following formula (1),
wherein X, Y, Z contains at least one unsaturated group.
2. The additive of claim 1, wherein the unsaturated group comprises at least one of an alkenyl group, an alkynyl group, a halogen, a cyano group, a siloxane group, an amino group, a phenyl group, a nitro group, a phosphate group, and a phosphite group.
3. The additive of claim 1 or 2, wherein each of X, Y, Z is independently selected fromAt least one of hydrogen, halogen, cyano, siloxy, amino, phenyl, nitro, phosphate, phosphite, and at least one of X, Y, Z is ∈ ->And/orWherein R is 1 、R 2 Each independently selected from at least one of hydrogen, halogen, cyano, siloxy, amino, phenyl, nitro, phosphate, phosphite; m and n are positive integers, and the values of m and n satisfy the following conditions: m is more than or equal to 1 and less than or equal to 3, n is more than or equal to 1 and less than or equal to 3.
4. An additive according to any one of claims 1-3, wherein the additive is selected from the group consisting of 1- (4-amino-but-2-enyl) -3, 5-difluoro- [1,3,5] triazine-2, 4, 6-trione, 1- (4-amino-but-2-ynyl) -3, 5-di-prop-2-ynyl- [1,3,5] triazine-2, 4, 6-trione, 1, 3-diallyl-5- (3-phenyl-allyl) - [1,3,5] triazine-2, 4, 6-trione, 1- (3-phenyl-prop-2-ynyl) -3, 5-di-prop-2-ynyl- [1,3,5] triazine-2, 4, 6-trione 1- [4- (allyl-dimethyl-silyl) -but-2-ynyl ] -3, 5-di-prop-2-ynyl- [1,3,5] triazine-2, 4, 6-trione, 1, 3-diallyl-5- (3-phenyl-allyl) - [1,3,5] triazine-2, 4, 6-trione, 1- (3-phenyl-prop-2-ynyl) -3, 5-di-prop-2-ynyl- [4, 6-trione, 1- (3, 5-dimethyl-silyl) -but-2, 4, 6-trione At least one of 5- (3, 5-diallyl-2, 4, 6-trioxo- [1,3,5] triazin-1-yl) -pent-3-enyl ester dimethyl phosphate, 5- { 3-allyl-5- [4- (allyl-dimethyl-silyl) -but-2-ynyl ] -2,4, 6-trioxo- [1,3,5] triazin-1-yl } -pent-3-enenitrile.
5. An electrolyte comprising a lithium salt, an organic solvent, and an additive, wherein the additive comprises a first additive, and wherein the first additive is the electrolyte additive of any one of claims 1-4.
6. The electrolyte according to claim 5, wherein the electrolyte further comprises a second additive selected from at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propylene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, lithium difluorosulfimide, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorooxalato phosphate, lithium bisoxalato borate, and methylene methane disulfonate;
and/or the lithium salt is selected from LiPF 6 One or more of lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide;
and/or the organic solvent is selected from at least one of ethylene carbonate, propylene carbonate and propylene carbonate; preferably, the mass ratio of the ethylene carbonate to the propylene carbonate is (15-35): (0-15): (10-80): (0-30).
7. The electrolyte according to claim 6, wherein the first additive is present in an amount of 0.02-3wt%, preferably 0.1-1wt%, based on 100% of the total mass of the electrolyte; the content of the second additive is 0-10wt%, preferably 0.3-6wt%; the lithium salt content is 11-14wt%, preferably 70-90wt%.
8. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte is the electrolyte of any one of claims 5-7.
9. The lithium ion battery of claim 8, wherein the active material of the positive electrode is a lithium nickel cobalt manganese oxide positive electrode material or a lithium cobalt oxide positive electrode material, preferably the active material of the positive electrode is a high nickel positive electrode material.
10. The lithium ion battery according to claim 8 or 9, wherein the active material of the negative electrode is a silicon material and/or a carbon material; preferably, the active material of the negative electrode is selected from at least one of carbon-coated silicon, silicon oxide, silicon-carbon mixture, or graphite.
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