CN115332628A - Lithium ion battery electrolyte, lithium ion battery and electric equipment - Google Patents
Lithium ion battery electrolyte, lithium ion battery and electric equipment Download PDFInfo
- Publication number
- CN115332628A CN115332628A CN202211158575.7A CN202211158575A CN115332628A CN 115332628 A CN115332628 A CN 115332628A CN 202211158575 A CN202211158575 A CN 202211158575A CN 115332628 A CN115332628 A CN 115332628A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- group
- lithium
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 81
- 239000003960 organic solvent Substances 0.000 claims abstract description 61
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical class N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910000077 silane Inorganic materials 0.000 claims abstract 2
- -1 1,3-propylene sultone Chemical class 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 6
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 6
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 6
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 4
- 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 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 3
- SMTJVGKZVGURTO-UHFFFAOYSA-N B(O)(O)OB(O)O.OCC(C)(CO)C Chemical compound B(O)(O)OB(O)O.OCC(C)(CO)C SMTJVGKZVGURTO-UHFFFAOYSA-N 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims description 3
- VIHAEDVKXSOUAT-UHFFFAOYSA-N but-2-en-4-olide Chemical compound O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000007770 graphite material Substances 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
- 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 claims description 3
- PMCYLLXGYKRQEL-UHFFFAOYSA-N CC=C.CC=C.CC=C.OP(O)(O)=O Chemical compound CC=C.CC=C.CC=C.OP(O)(O)=O PMCYLLXGYKRQEL-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- 229940125904 compound 1 Drugs 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 229940125782 compound 2 Drugs 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229940126214 compound 3 Drugs 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LCHWKMAWSZDQRD-UHFFFAOYSA-N silylformonitrile Chemical compound [SiH3]C#N LCHWKMAWSZDQRD-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a lithium ion battery electrolyte, a lithium ion battery and electric equipment, and belongs to the field of battery manufacturing. The lithium ion battery electrolyte comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a bipyrimidine derivative with a structural general formula shown as a formula I: R1-R6 are independently selected from one of hydrogen atoms, fluorine atoms, cyano groups, silane and C1-C6 alkyl or fluorine-containing alkyl, and the lithium ion battery electrolyte can solve the problem of poor high-low temperature electrical properties of the battery under the condition of ensuring the cycle performance and safety performance of the battery.
Description
Technical Field
The application relates to the field of battery manufacturing, in particular to a lithium ion battery electrolyte, a lithium ion battery and electric equipment.
Background
In the prior art, lithium ion batteries are widely used due to the advantages of high energy density, long cycle life and the like, but as the lithium ion batteries are applied to new energy automobiles, the batteries are required to have not only longer cycle service life, but also better high-low temperature electrical properties and safety performance.
Based on this, technical personnel develop an additive suitable for lithium ion battery electrolyte, which can ensure that the battery has a longer cycle life and better safety performance, but the current additive is difficult to give consideration to the high and low temperature electrical properties of the battery, especially in high voltage batteries with more than 4.2V, so that the application of the lithium ion battery in the field of new energy automobiles is limited.
Disclosure of Invention
An object of the application is to provide a lithium ion battery electrolyte, a lithium ion battery and an electric device, which can solve the problem of poor high and low temperature electrical properties of the battery under the condition of ensuring the cycle performance and the safety performance of the battery.
The embodiment of the application is realized as follows:
in a first aspect, an embodiment of the present application provides an electrolyte for a lithium ion battery, including an organic solvent, a lithium salt, and an additive, where the additive includes a bipyrimidine derivative having a general structural formula shown in formula I:
wherein, R1 to R6 are independently selected from one of hydrogen atom, fluorine atom, cyano, silane and C1 to C6 alkyl or fluorine-containing alkyl.
In the technical scheme, the electrolyte contains the additive components with the structural general formula, on one hand, the bipyrimidine derivative can form a stable and thin CEI film on the surface of a positive electrode through a plurality of functional groups of the bipyrimidine derivative, so that the increase of the interface impedance of the battery is inhibited, and the cycle performance and the high-low temperature electrical performance of the battery are improved; on the other hand, because a plurality of alkalescent N atoms exist in the bipyrimidine derivative, the alkalescent N atoms can neutralize part of HF generated in the electrolyte, so that the acidity of the electrolyte is reduced, and the function of protecting an electrode material is achieved. Through the synergistic effect of the two aspects, in a high-voltage battery and a low-voltage battery, the bipyrimidine derivative can effectively avoid the damage of electrolyte components to an electrode material and inhibit the increase of interfacial impedance of the battery, so that the problem of poor high-temperature and low-temperature electrical properties of the battery can be solved under the condition of ensuring the cycle performance and the safety performance of the battery.
In some alternative embodiments, R1 to R6 are each independently one selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, triethylsilane, methyl, ethyl, propyl, phenyl, ethenyl, propenyl, ethynyl, propynyl, fluoromethyl, fluoroethyl, fluoropropyl, fluoroethenyl, fluoropropenyl, fluorobutenyl, and fluorophenyl.
In the technical scheme, the R1-R6 are limited in the range, so that the battery has better cycle performance and high-low temperature electrical properties compared with other structures.
In some alternative embodiments, R1 to R6 are each independently selected from one of a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, methyl group, ethyl group, propyl group, phenyl group, ethenyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, and fluorophenyl group.
In the technical scheme, the R1-R6 are limited in the range, and compared with other structures, the cycle performance and the high-low temperature electrical performance of the battery can be further improved.
In some alternative embodiments, the weight percentage of the bipyrimidine derivative in the additive is 0.5-5%.
In the above technical solution, the usage of the bipyrimidine derivative is limited to the above range because: if the usage amount of the bipyrimidine derivative is too low, the cycle performance and the high-low temperature electrical performance of the battery cannot be effectively improved; if the usage amount of the bipyrimidine derivative is too high, the lithium salt in the electrolyte is decomposed due to too high alkalinity of the electrolyte, and the impedance of an interface film (CEI film) is increased rapidly, so that the polarization of the battery is too large, and the electrical performance of the battery is affected.
In some alternative embodiments, the additive further comprises one or more of vinyl sulfate, fluoroethylene carbonate, 1,3-propylene sultone, ethylene carbonate, 1,3-propane sultone, methylene methyl disulfonate, allyl isocyanate, triallylisocyanurate, pinacol diborate, neopentyl glycol diborate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trimethylsilyl) phosphite, and tripropylene phosphate.
In the technical scheme, the additive also contains the components, so that the electrolyte can be endowed with more functions, and the electrical property of the battery is comprehensively improved.
In some optional embodiments, the additive is present in the lithium ion battery electrolyte in an amount of 0.1 to 20% by mass.
In the technical scheme, the dosage of the additive is limited in the range, so that the additive has a proper dosage, and the electrical performance of the battery can be better improved.
In some alternative embodiments, the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, carboxylate, fluoroether, 3,3,3-propylene trifluorocarbonate, methyl trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether fluorocarbonate, and fluorocarboxylate.
In the technical scheme, the scheme of the application can be well suitable for the multiple organic solvent systems, and more implementable schemes are provided, so that the popularization and the application are facilitated.
In some alternative embodiments, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorosulfonimide, lithium difluorobis (oxalato) phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (oxalato) borate;
optionally, the mass percentage of the lithium salt in the lithium ion battery electrolyte is 10-20%.
In the technical scheme, the scheme of the application can be well suitable for various lithium salt systems, and more implementable schemes are provided, so that the popularization and the application are facilitated.
Further, limiting the amount of the lithium salt to the above range enables the lithium salt to have an appropriate amount ratio, thereby ensuring the charge and discharge performance of the battery.
In a second aspect, embodiments of the present application provide a lithium ion battery, which includes a case, an electrode assembly, and the lithium ion battery electrolyte provided in the embodiments of the first aspect. The electrode assembly is accommodated in the case; the lithium ion battery electrolyte is contained within the housing.
In the above technical scheme, the lithium ion battery includes the lithium ion battery electrolyte provided in the embodiment of the first aspect, and in the high-low voltage battery, the lithium ion battery electrolyte can effectively avoid damage of electrolyte components to an electrode material and can inhibit increase of interfacial impedance of the battery, so that the problem of poor high-low temperature electrical properties of the battery can be solved under the condition of ensuring cycle performance and safety performance of the battery.
In some alternative embodiments, in the battery positive electrode, at least one of the following conditions (a) to (c) is satisfied:
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x + y + z =1;
(b) The positive active material includes LiFe x Mn 1-x PO 4 Wherein, 0<x≤1；
(c) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
In the technical scheme, the scheme of the application can be well suitable for various anode active material systems, and more implementable schemes are provided, so that the popularization and the application are facilitated.
In some alternative embodiments, the negative active material in the battery negative electrode comprises one or more of a graphite material, a silicon carbon composite, a silica, and a graphite composite.
In the technical scheme, the scheme of the application can be well suitable for the various anode active material systems, and more implementable schemes are provided, so that the popularization and the application are facilitated.
In a third aspect, an embodiment of the present application provides an electric device, which includes the lithium ion battery provided in the embodiment of the second aspect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.
In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents both "unit of measure" of "numerical value a" and "numerical value b".
In the prior art, although the current electrolyte can ensure the cycle performance and the safety performance of the battery, the high and low temperature electrical performance of the battery is difficult to be considered, particularly for the battery under high pressure and high temperature, the current electrolyte has the problems of poor pressure resistance, high oxidation activity of the battery anode and the like, and in addition, the decomposition and acid production efficiency of the electrolyte component under high temperature and high pressure is high, so that the battery has the problems of high internal resistance, high gas production expansion and the like.
Based on the above, the inventors provide an electrolyte containing an additive with a specific structure, wherein the additive in the electrolyte can form a stable and thin CEI film on the surface of a positive electrode to passivate a positive electrode interface, and can neutralize part of HF in the electrolyte, so that the problem of poor high-temperature and low-temperature electrical properties of a battery can be solved while the cycle performance and safety performance of the battery are ensured.
The following describes a lithium ion battery electrolyte, a lithium ion battery, and an electric device in an embodiment of the present application.
In a first aspect, an embodiment of the present application provides an electrolyte for a lithium ion battery, including an organic solvent, a lithium salt, and an additive, where the additive includes a bipyrimidine derivative having a general structural formula shown in formula I:
wherein, R1 to R6 are independently selected from one of hydrogen atom, fluorine atom, cyano, silane and C1 to C6 alkyl or fluorine-containing alkyl.
In the application, the electrolyte contains the additive component with the structural general formula, on one hand, the bipyrimidine derivative can form a stable and thin CEI film passivation positive electrode interface on the surface of a positive electrode through a plurality of functional groups of the bipyrimidine derivative, so that the increase of the interface impedance of the battery is inhibited, and the cycle performance and the high-low temperature electrical performance of the battery are improved; on the other hand, because a plurality of alkalescent N atoms exist in the bipyrimidine derivative, the alkalescent N atoms can neutralize part of HF generated in the electrolyte, so that the acidity of the electrolyte is reduced, and the function of protecting electrode materials is achieved. Through the synergistic effect of the two aspects, in a high-voltage battery and a low-voltage battery, the bipyrimidine derivative can effectively avoid the damage of electrolyte components to an electrode material and inhibit the increase of interfacial impedance of the battery, so that the problem of poor high-temperature and low-temperature electrical properties of the battery can be solved under the condition of ensuring the cycle performance and the safety performance of the battery.
It should be noted that the bipyrimidine derivative provided by the present application has at least four N atoms, and thus has a more significant effect in neutralizing HF generated in the electrolyte than other electrolyte additives (only one or 2 additives are common).
It should be noted that the structure of the bipyrimidine derivative is not limited, and can be adjusted according to actual needs.
As an example, R1 to R6 are each independently one selected from a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, triethylsilane, methyl group, ethyl group, propyl group, phenyl group, vinyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorovinyl group, fluoropropenyl group, fluorobutenyl group, and fluorophenyl group.
In this embodiment, when R1 to R6 are limited to the above range, the battery can have better cycle performance and high and low temperature electrical properties than when other structures are used.
It is understood that the structure thereof may be further defined in consideration of the effect of the bipyrimidine derivative on improvement of the electrical properties of the battery.
As an example, R1 to R6 are each independently one selected from a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, methyl group, ethyl group, propyl group, phenyl group, vinyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, and fluorophenyl group.
In this embodiment, R1 to R6 are limited to the above range, and the cycle performance and the high and low temperature electrical performance of the battery can be further improved as compared with the case of adopting another structure.
As an example, the bipyrimidine derivative includes one or more of the following compounds.
It is understood that the amount of the bipyrimidine derivative used may have an influence on the electrical properties of the battery, and the amount of the bipyrimidine derivative used may be limited in consideration of the electrical properties of the battery.
As an example, the mass percentage of the bipyrimidinyl derivative in the additive is 0.5 to 5%, such as but not limited to, any one of 0.5%, 1%, 2%, 3%, 4%, and 5% or a range between any two.
In this embodiment, the reason why the usage of the bipyrimidine derivative is limited to the above range is that: if the usage amount of the bipyrimidine derivative is too low, the cycle performance and the high-low temperature electrical performance of the battery cannot be effectively improved; if the usage amount of the bipyrimidine derivative is too high, the lithium salt in the electrolyte is decomposed due to too high alkalinity of the electrolyte, and the impedance of an interface film (CEI film) is increased rapidly, so that the polarization of the battery is too large, and the electrical performance of the battery is affected.
It is noted that the components of the additive may be adjusted in order to impart more abundant functions to the electrolyte.
As an example, the additive further includes one or more of vinyl sulfate, fluoroethylene carbonate, 1,3-propylene sultone, ethylene carbonate, 1,3-propane sultone, methylene methanedisulfonate, allyl isocyanate, triallyl isocyanurate, pinacol diborate, neopentyl glycol diborate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trimethylsilyl) phosphite, and triallyl phosphate.
In this embodiment, the additive further contains the above-mentioned components, and thus can provide more functions to the electrolyte, thereby more comprehensively improving the electrical properties of the battery.
As an example, the mass percentage of the additive in the electrolyte of the lithium ion battery is 0.1 to 20%, such as but not limited to any one of 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 10%, 15% and 20% or a range value between any two.
In this embodiment, limiting the amount of the additive to the above range enables the additive to have an appropriate amount, thereby enabling the electrical properties of the battery to be improved more.
It should be noted that the kind of the organic solvent is not limited, and can be adjusted according to actual needs.
As an example, the organic solvent includes one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, carbonate esters, carboxylic acid esters, fluoroether, 3,3,3-propylene trifluorocarbonate, methyl trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether fluorocarbonate, and fluorocarboxylic acid esters.
In the embodiment, the scheme of the application can be well suitable for the multiple organic solvent systems, and more implementable schemes are provided, so that the popularization and the application are facilitated.
It should be noted that the type of the lithium salt is not limited, and can be adjusted according to actual needs.
As an example, the lithium salt includes one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorosulfonimide, lithium difluorobis (oxalato) phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (oxalato borate;
optionally, the mass percentage of the lithium salt in the lithium ion battery electrolyte is 10-20%, such as but not limited to 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% and 20%, or any value or range between any two.
In this embodiment, the scheme of the present application can be better applied to the above-mentioned multiple lithium salt systems, and more implementable schemes are provided, thereby facilitating popularization and application.
Further, limiting the amount of the lithium salt to the above range enables the lithium salt to have an appropriate amount ratio, thereby ensuring the charge and discharge performance of the battery.
In a second aspect, embodiments of the present application provide a lithium ion battery, which includes a case, an electrode assembly, and the lithium ion battery electrolyte provided in the embodiments of the first aspect. An electrode assembly is accommodated in the case; the lithium ion battery electrolyte is contained within the housing.
It should be noted that the electrode assembly, also called as a battery cell, includes a positive electrode plate, a separator and a negative electrode plate, which are sequentially disposed.
In this application, lithium ion battery is including the lithium ion battery electrolyte that the embodiment of the first aspect provided, in high-low voltage battery, this lithium ion battery electrolyte homoenergetic effectively avoids electrolyte composition to cause the damage and can restrain the increase of battery interfacial impedance to can compromise the not good enough problem of high low temperature electrical properties of solution battery under the circumstances of the cycle performance and the security performance of guaranteeing the battery.
As an example, in the battery positive electrode, at least one of the following conditions (a) to (c) is satisfied:
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x + y + z =1;
(b) The positive active material includes LiFe x Mn 1-x PO 4 Wherein, 0<x≤1；
(c) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
In this embodiment, the scheme of the application can be better suitable for the above-mentioned multiple positive active material systems, provides more implementable schemes, and is convenient for popularization and application.
It is understood that the structure thereof may be further defined in consideration of the influence of the positive electrode active material on the electrical properties of the battery.
As an example, the positive active material includes LiNi 0.8 Co 0.15 Al 0.05 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiCoO 2 And LiFePO 4 One or more of (a).
As one example, in a battery anode, the anode active material includes one or more of a graphite material, a silicon carbon composite, a silica, and a graphite composite.
In this embodiment, the scheme of the application can be better applied to the above-mentioned multiple negative active material systems, and more practical schemes are provided, so that the popularization and application are facilitated.
The structures not specifically described in the lithium ion battery may be arranged according to the conventional options in the art.
In a third aspect, an embodiment of the present application provides an electric device, which includes the lithium ion battery provided in the embodiment of the second aspect.
In this embodiment, the type of the electric device is not limited, and examples of the electric device include a mobile phone, a portable device, a notebook computer, a battery car, an electric car, a ship, a spacecraft, an electric toy, an energy storage device, and an electric tool.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which comprises the following steps:
ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DEC) in a mass ratio of 2:5:3, mixing to obtain a mixed organic solvent; to the mixed organic solvent were added 0.1% of compound 1 and 13.5% of lithium hexafluorophosphate (LiPF) 6 ) Obtaining electrolyte; wherein the mass ratio of the mixed organic solvent is 86.4%.
Example 2
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 0.5% of compound 1 was added to the mixed organic solvent, and the amount was varied by adjusting the amount of the mixed organic solvent.
Example 3
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: compound 1 was added to the mixed organic solvent in an amount of 1%, and the amount was varied by adjusting the amount of the mixed organic solvent.
Example 4
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: compound 1 was added to the mixed organic solvent at 2%, and the amount was varied by adjusting the amount of the mixed organic solvent.
Example 5
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 4% of Compound 1 was added to the mixed organic solvent, and the amount was varied by adjusting the amount of the mixed organic solvent.
Example 6
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: compound 1 was added to the mixed organic solvent at 5% and the amount was varied to adjust the amount of the mixed organic solvent.
Example 7
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: compound 1 was added to the mixed organic solvent at 6%, and the amount was adjusted by changing the amount of the mixed organic solvent.
Example 8
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 0.5% of compound 1 and 2% of compound 3 were added to the mixed organic solvent, and the amount was varied by adjusting the amount of the mixed organic solvent.
Example 9
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 0.5% of compound 2 and 2% of compound 4 are added to the mixed organic solvent, the amount of which is varied by the amount of the mixed organic solvent.
Example 10
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 0.5% of compound 1, 1% of compound 5 and 2% of compound 7 were added to the mixed organic solvent, and the amount was adjusted by changing the amount of the mixed organic solvent.
Example 11
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: 1% of compound 1, 1.5% of compound 3, 1% of compound 4 and 2% of compound 8 are added to the mixed organic solvent, the amount of the mixed organic solvent being varied.
Example 12
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 4 in that: to the mixed organic solvent were added 2% of compound 2, 5% of fluoroethylene carbonate (FEC) and 13.5% of lithium hexafluorophosphate (LiPF) 6 ) The amount of the organic solvent is adjusted by changing the amount of the organic solvent.
Example 13
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which comprises the following steps:
ethylene Carbonate (EC), propylene Carbonate (PC) and Ethyl Methyl Carbonate (EMC) are mixed according to the mass ratio of 1:1:8, mixing to obtain a mixed organic solvent; to the mixed organic solvent were added 1% of compound 1, 2% of compound 3, and 12.5% of lithium hexafluorophosphate (LiPF) 6 ) 2% of lithium bis (fluorosulfonyl) imide (LiFSI), 5% of fluoroethylene carbonate (FEC) and 1% of ethylene sulfate (DTD) to obtain an electrolyte; wherein the mass ratio of the mixed organic solvent is 76.5%.
Example 14
The embodiment of the present application provides a method for preparing an electrolyte for a lithium ion battery, and the differences of the remaining embodiments 13 are as follows: 0,5% Compound 2, 1.5% Compound 4, 1% Compound 8, 12.5% lithium hexafluorophosphate (LiPF) was added to the mixed organic solvent 6 ) 2% lithium bis-fluorosulfonylimide (LiFSI), 5% fluoroethylene carbonate (FEC) and 1% ethylene sulfate (DTD).
Example 15
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which comprises the following steps:
ethylene Carbonate (EC), 3,3,3-propylene trifluorocarbonate (FPC) and methyl trifluoroethyl carbonate (FEMC) are mixed according to a mass ratio of 2:2:6, mixing to obtain a mixed organic solvent; to the mixed organic solvent, 2% of compound 1, 15% of lithium hexafluorophosphate (LiPF) was added 6 ) 3% of fluoroethylene carbonate (FEC) and 3% of 1,3-Propane Sultone (PS) to obtain an electrolyte; wherein the mass ratio of the mixed organic solvent is 77%.
Example 16
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 15 in that: the amount of 2% compound 1 was changed to 1% compound 2 and 1% compound 7, and the amount was adjusted by changing the amount of the mixed organic solvent.
Example 17
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 15 in that: the amount of compound 1 was changed to 0.2% to compound 5 and 2% to compound 6, and the amount was adjusted by changing the amount of the mixed organic solvent.
Example 18
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which comprises the following steps:
ethylene Carbonate (EC), methyl trifluoroethyl carbonate (FEMC) and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (FEPE) are mixed according to the mass ratio of 2:6:2, mixing to obtain a mixed organic solvent; to the mixed organic solvent, 1.5% of compound 3 and 13% of lithium hexafluorophosphate (LiPF) were added 6 ) 0.5% of lithium difluorophosphate (LiPO) 2 F 2 ) 3% of fluoroethylene carbonate (FEC) and 1% of 1,3-Propylene Sultone (PST) to obtain an electrolyte; wherein the mass ratio of the mixed organic solvent is 81%.
Example 19
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 18 in that: 1.5% of compound 3 was replaced with 1% of compound 2 and 0.5% of compound 5, and the amount was varied by mixing the amounts of the organic solvents.
Example 20
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 18 in that: 1.5% of compound 3 was replaced with 1% of compound 4 and 1% of compound 8, and the amount was varied by mixing the amounts of the organic solvents.
Comparative example 1
The comparative example of the application provides a preparation method of an electrolyte of a lithium ion battery, which is different from the electrolyte of the example 1 in that: compound 1 was not added to the mixed organic solvent at 0.1%, and the amount was varied by adjusting the amount of the mixed organic solvent.
Comparative example 2
The comparative example of the application provides a preparation method of an electrolyte of a lithium ion battery, which is different from the electrolyte of the example 12 in that: compound 2 was not added to the mixed organic solvent at 2%, and the amount was varied by adjusting the amount of the mixed organic solvent.
Comparative example 3
The comparative example of the application provides a preparation method of an electrolyte of a lithium ion battery, which is different from the electrolyte of the example 13 in that: no 1% of compound 1 and 2% of compound 3 were added to the mixed organic solvent, the amount of which was varied by adjusting the amount of the mixed organic solvent.
Comparative example 4
The comparative example of the application provides a preparation method of an electrolyte of a lithium ion battery, which is different from the electrolyte of the example 15 in that: compound 1 was not added to the mixed organic solvent at 2%, and the amount was varied by adjusting the amount of the mixed organic solvent.
Comparative example 5
The comparative example of the application provides a preparation method of an electrolyte of a lithium ion battery, which is different from the electrolyte of the example 18 in that: compound 3 was not added to the mixed organic solvent in an amount of 1.5%, and the amount was varied by adjusting the amount of the mixed organic solvent.
For ease of understanding, the collective arrangement is made by the following table 1.
The amount of the organic solvent used was the balance excluding the amounts described in table 1 below.
TABLE 1 composition Table of examples and comparative examples
Test example 1
Electrical Performance testing
The test method comprises the following steps:
the lithium ion battery electrolytes prepared in examples 1 to 20 and comparative examples 1 to 5 were assembled into batteries and numbered correspondingly, and then the capacity retention rate of the batteries was measured at 25 ℃ and 45 ℃ for 300 cycles, and the capacity recovery rate and the thickness expansion rate of the batteries were measured at 60 ℃ and 7 days of storage.
Wherein the content of the first and second substances,
the assembly of the cell was carried out as follows:
s1, according to a weight ratio of 97.8:1.0: liNi mixed at a mass ratio of 1.2 0.8 Co 0.1 Mn 0.1 O 2 Or LiNi 0.5 Mn 1.5 O 4 (positive electrode active material), conductive carbon black (conductive agent) and polyvinylidene fluoride (binder), dispersed in N-methyl-2-pyrrolidone to obtain positive electrode slurry; then, uniformly coating the anode slurry on two sides of the aluminum foil; then, after drying, rolling and vacuum drying in sequence, an aluminum outgoing line is welded on the positive plate by an ultrasonic welding machine to obtain the positive plate with the thickness of 125 μm.
S2, according to a ratio of 95:1.5:1.5:2, mixing graphite or a silicon-carbon composite material (a negative electrode active material), conductive carbon black (a conductive agent), styrene butadiene rubber and carboxymethyl cellulose (a binder) in a mass ratio, and dispersing in deionized water to obtain negative electrode slurry; then, coating the negative electrode slurry on two sides of the copper foil; then, after drying, rolling and vacuum drying in sequence, a nickel outgoing line is welded on the cathode sheet by an ultrasonic welding machine to obtain a cathode sheet with the thickness of 125 μm.
S3, winding the prepared positive plate, the prepared negative plate and the prepared ionic diaphragm (PP/PE/PP three-layer composite diaphragm) to prepare a bare cell, then injecting the bare cell, the shell and the lithium ion battery electrolyte group prepared in the embodiments 1-20 and the comparative examples 1-5 into the dried battery, and completing battery assembly through packaging, standing, formation, shaping and capacity test.
The electrode material systems of examples 1 to 14 and comparative examples 1 to 3 were LiNi 0.8 Co 0.1 Mn 0.1 O 2 Silicon carbon; the electrode material systems corresponding to examples 15 to 20 and comparative examples 4 to 5 were LiNi 0.5 Mn 1.5 O 4 Graphite.
The test of the corresponding electrical parameters of the battery and the corresponding calculation formula are as follows:
capacity retention test of battery at 25 ℃ cycling for 300 weeks: the cell was left to stand at 25 ℃ with LiNi 0.8 Co 0.1 Mn 0.1 O 2 The silicon-carbon battery has a charge-discharge voltage interval of 2.5-4.2V, while LiNi 0.5 Mn 1.5 O 4 The graphite battery was subjected to charge-discharge cycles using a 1C current in a charge-discharge voltage range of 3.5 to 4.8V, and the discharge retention capacity of the 300 th cycle was recorded.
Capacity retention test of the battery at 45 ℃ and 300 weeks cycling: the cell was left at 45 ℃ with LiNi 0.8 Co 0.1 Mn 0.1 O 2 The silicon-carbon battery has a charge-discharge voltage interval of 2.5-4.2V, and LiNi 0.5 Mn 1.5 O 4 The graphite battery was subjected to charge-discharge cycles using a 1C current in a charge-discharge voltage range of 3.5 to 4.8V, and the discharge retention capacity of the 300 th cycle was recorded.
Thickness swell and capacity recovery tests of the battery stored at 60 ℃ for 7 days: the fully charged battery was stored at 60 ℃ for 7 days, and the battery was subjected to capacity recovery at room temperature (25 ℃), wherein LiNi 0.8 Co 0.1 Mn 0.1 O 2 The silicon-carbon battery has a charge-discharge voltage interval of 2.5-4.2V, and LiNi 0.5 Mn 1.5 O 4 The graphite battery is subjected to charge-discharge cycle for 5 weeks by using 1C current in a charge-discharge voltage interval of 3.5-4.8V, and the discharge retention capacity and recovery capacity of the battery are tested.
The calculation formula is as follows:
capacity retention (%) at 300 cycles = (300-th discharge retention capacity/1-th cycle discharge capacity) × 100%;
capacity recovery (%) = recovery capacity/initial capacity × 100%;
thickness expansion (%) = (thickness measured thermally-initial thickness)/initial thickness × 100%.
TABLE 2 Electrical Property test results
Referring to table 2, from the results of the electrical property tests of examples 1 to 11 and comparative example 1, it can be seen that the capacity retention rate of the battery prepared by using the electrolyte containing at least one bipyrimidine derivative provided by the present application at 25 ℃, 45 ℃ and 300 weeks in cycle, and the capacity recovery rate and the thickness expansion rate of the battery stored at 60 ℃ for 7 days are both significantly improved.
From the results of the electrical characteristics tests of examples 1 to 7, it can be seen that when the mass ratio of the additive is in the range of 0.5% to 5%, the results of the electrical characteristics tests of the battery are better than those of the battery in other ranges.
From the results of the electrical property tests of example 12 and example 4, it can be seen that when the additive further comprises the additional additive provided herein, the electrical properties of the battery can be further improved through the synergistic effect of the various additive components.
From the electrical property test results of examples 13 and 14 and comparative example 3, it can be seen that the electrolyte contains at least one bipyrimidine derivative provided by the present application, and the capacity retention rate of the prepared battery at 25 ℃, 45 ℃ and 300 weeks in cycle, and the capacity recovery rate and the thickness expansion rate of the battery at 60 ℃ and 7 days in storage are both significantly improved.
From the electrical property test results of examples 15 to 17 and comparative example 4, it can be seen that the electrolyte contains at least one bipyrimidine derivative provided by the present application, and the capacity retention rate of the prepared battery at 25 ℃ and 45 ℃ for 300 cycles, and the capacity recovery rate and the thickness expansion rate of the battery at 60 ℃ for 7 days storage are both significantly improved.
As can be seen from the electrical property test results of examples 18-20 and comparative example 5, the electrolyte contains at least one bipyrimidine derivative provided by the application, and the capacity retention rate of the prepared battery at 25 ℃, 45 ℃ and 300 weeks of circulation, and the capacity recovery rate and the thickness expansion rate of the battery stored at 60 ℃ for 7 days are both obviously improved.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (12)
1. The lithium ion battery electrolyte is characterized by comprising an organic solvent, a lithium salt and an additive, wherein the additive comprises a bipyrimidine derivative with a structural general formula shown as a formula I:
wherein, R1-R6 are independently selected from one of hydrogen atom, fluorine atom, cyano-group, silane and C1-C6 alkyl or fluorine-containing alkyl.
2. The lithium ion battery electrolyte of claim 1 wherein R1 to R6 are each independently selected from one of a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, triethylsilane, methyl, ethyl, propyl, phenyl, ethenyl, propenyl, ethynyl, propynyl, fluoromethyl, fluoroethyl, fluoropropyl, fluoroethenyl, fluoropropenyl, fluorobutenyl, and fluorophenyl group.
3. The lithium ion battery electrolyte of claim 2 wherein R1 to R6 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, trimethylsilane, a methyl group, an ethyl group, a propyl group, a phenyl group, a vinyl group, a propenyl group, an ethynyl group, a propynyl group, a fluoromethyl group, a fluoroethyl group, and a fluorophenyl group.
4. The lithium ion battery electrolyte of any one of claims 1-3 wherein the mass percent of the bipyrimidine derivative in the additive is 0.5-5%.
5. The lithium ion battery electrolyte of any of claims 1-3 wherein the additive further comprises one or more of vinyl sulfate, fluoroethylene carbonate, 1,3-propylene sultone, ethylene carbonate, 1,3-propane sultone, methylene methyl disulfonate, allyl isocyanate, triallyl isocyanurate, pinacol diborate, neopentyl glycol diborate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trimethylsilyl) phosphite, and tripropylene phosphate.
6. The lithium ion battery electrolyte of claim 5, wherein the additive is present in the lithium ion battery electrolyte in an amount of 0.1 to 20% by mass.
7. The lithium ion battery electrolyte of any of claims 1-3, wherein the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, carboxylate, fluoroether, 3,3,3-propylene trifluorocarbonate, methyl trifluoroethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether fluorocarbonate, and fluorocarboxylate.
8. The lithium ion battery electrolyte of any of claims 1-3, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis-fluorosulfonylimide, lithium difluorobis-oxalato-phosphate, lithium tetrafluorooxalato-phosphate, lithium difluorooxalato-borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis-oxalato-borate;
optionally, the mass percentage of the lithium salt in the lithium ion battery electrolyte is 10 to 20%.
9. A lithium ion battery, comprising:
a housing;
an electrode assembly housed within the case; and
the lithium ion battery electrolyte of any of claims 1-8 contained within the housing.
10. The lithium ion battery according to claim 9, wherein at least one of the following conditions (a) to (c) is satisfied in the battery positive electrode:
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x + y + z =1;
(b) The positive active material includes LiFe x Mn 1-x PO 4 Wherein, 0<x≤1；
(c) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
11. The lithium ion battery of claim 9, wherein in the battery negative electrode, the negative active material comprises one or more of a graphite material, a silicon carbon composite, a silicon oxide, and a graphite composite.
12. An electric consumer characterized in that it comprises a lithium ion battery according to any one of claims 9 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211158575.7A CN115332628A (en) | 2022-09-22 | 2022-09-22 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211158575.7A CN115332628A (en) | 2022-09-22 | 2022-09-22 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115332628A true CN115332628A (en) | 2022-11-11 |
Family
ID=83914694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211158575.7A Pending CN115332628A (en) | 2022-09-22 | 2022-09-22 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115332628A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116053590A (en) * | 2023-03-28 | 2023-05-02 | 广汽埃安新能源汽车股份有限公司 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
| CN117638083A (en) * | 2024-01-24 | 2024-03-01 | 宁德新能源科技有限公司 | Lithium ion battery and electronic device |
-
2022
- 2022-09-22 CN CN202211158575.7A patent/CN115332628A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116053590A (en) * | 2023-03-28 | 2023-05-02 | 广汽埃安新能源汽车股份有限公司 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
| CN117638083A (en) * | 2024-01-24 | 2024-03-01 | 宁德新能源科技有限公司 | Lithium ion battery and electronic device |
| CN117638083B (en) * | 2024-01-24 | 2024-04-30 | 宁德新能源科技有限公司 | Lithium ion battery and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113839093A (en) | Non-aqueous electrolyte of lithium ion battery and application thereof | |
| CN109728340B (en) | Lithium ion battery | |
| CN112531212B (en) | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery | |
| CN111883839B (en) | High-voltage electrolyte and lithium ion battery based on same | |
| KR20200103807A (en) | Additive for battery electrolyte, lithium ion battery electrolyte, lithium ion battery | |
| CN111525190B (en) | Electrolyte and lithium ion battery | |
| CN110265622B (en) | Positive electrode plate and lithium ion secondary battery | |
| CN115332628A (en) | Lithium ion battery electrolyte, lithium ion battery and electric equipment | |
| CN113130992B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN109004275B (en) | Electrolyte solution and secondary battery | |
| CN111129590A (en) | High-voltage lithium ion battery non-aqueous electrolyte and high-voltage lithium ion battery | |
| CN111129598A (en) | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| JP2021534555A (en) | Lithium ion secondary battery | |
| CN111834665B (en) | High-nickel ternary lithium ion battery electrolyte and lithium ion battery | |
| CN113078358A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN110911754B (en) | Lithium ion battery electrolyte and preparation method thereof | |
| CN114552007A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN113078356B (en) | High-voltage lithium cobalt oxide lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN112531213A (en) | Non-aqueous electrolyte with high-temperature characteristics and normal-temperature cycle, application thereof and lithium ion battery | |
| CN114605289B (en) | Carbamate compound for nonaqueous electrolyte and application thereof | |
| CN113889667B (en) | High-voltage electrolyte adaptive to lithium cobaltate battery capable of being charged quickly and application of high-voltage electrolyte | |
| CN114520371B (en) | Nonaqueous electrolyte and lithium ion battery comprising same | |
| CN114464889A (en) | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery thereof | |
| CN114464886A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN114520370A (en) | Lithium ion battery electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |