CN115395100A - Lithium ion battery electrolyte, lithium ion battery and electric equipment - Google Patents
Lithium ion battery electrolyte, lithium ion battery and electric equipment Download PDFInfo
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- CN115395100A CN115395100A CN202211170244.5A CN202211170244A CN115395100A CN 115395100 A CN115395100 A CN 115395100A CN 202211170244 A CN202211170244 A CN 202211170244A CN 115395100 A CN115395100 A CN 115395100A
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- Prior art keywords
- lithium
- ion battery
- lithium ion
- electrolyte
- additive
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 85
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 239000000654 additive Substances 0.000 claims abstract description 47
- 230000000996 additive effect Effects 0.000 claims abstract description 47
- -1 C6-C12 cycloolefine Chemical group 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 9
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims abstract description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 239000011737 fluorine Chemical group 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 31
- 150000001875 compounds Chemical group 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 claims description 3
- ODMITNOQNBVSQG-UHFFFAOYSA-N ethyl 2-fluoropropanoate Chemical compound CCOC(=O)C(C)F ODMITNOQNBVSQG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- IRWIXUQVVIFUPL-UHFFFAOYSA-N propyl 2-fluoroacetate Chemical compound CCCOC(=O)CF IRWIXUQVVIFUPL-UHFFFAOYSA-N 0.000 claims description 3
- LXPTXVYIIYSSHU-UHFFFAOYSA-N propyl 2-fluoropropanoate Chemical compound CCCOC(=O)C(C)F LXPTXVYIIYSSHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- VRSRNLHMYUACMN-UHFFFAOYSA-H trilithium;hexafluoroaluminum(3-) Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[F-].[F-].[Al+3] VRSRNLHMYUACMN-UHFFFAOYSA-H 0.000 claims description 3
- ZRPFJWDFNLWWOX-UHFFFAOYSA-N C(O)(=O)F.C=CC Chemical compound C(O)(=O)F.C=CC ZRPFJWDFNLWWOX-UHFFFAOYSA-N 0.000 claims 1
- HRSNTDPZHQCOGI-UHFFFAOYSA-N carbonyl difluoride ethene Chemical compound C=C.C(=O)(F)F HRSNTDPZHQCOGI-UHFFFAOYSA-N 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 25
- 239000011029 spinel Substances 0.000 abstract description 8
- 229910052596 spinel Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 150000002825 nitriles Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 239000012046 mixed solvent Substances 0.000 description 13
- 229940125904 compound 1 Drugs 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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 has a structural general formula shown as a formula I: R1-R4 are independently selected from one of hydrogen atoms, fluorine substituted or unsubstituted C1-C6 chain alkyl, C3-C12 naphthenic base, C2-C6 alkylene or alkyne, C6-C12 cycloolefine, cyano, C1-C5 nitrile, methoxy, ethoxy, phenyl, benzene ring derivative groups and five-membered or six-membered heterocyclic groups, and the lithium ion battery electrolyte can solve the problem that electrolyte components easily damage the spinel structure of the material under high pressure conditions to a certain extent, thereby improving the compatibility of the electrolyte and the electrode material with the spinel structure and further ensuring the electrical 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, the spinel-structured electrode material has the advantages of high energy density, high pressure resistance, good high-temperature cycling stability and the like, and is widely applied to the manufacture of lithium ion batteries. However, in the process of charging and discharging the existing electrolyte under the condition of high voltage (more than 4.5V), the problems of unstable electrolyte components and easy damage to the spinel structure of the material exist, so that the compatibility of the electrolyte and the electrode material with the spinel structure is poor, and the electrical performance of the battery is influenced.
Disclosure of Invention
An object of this application is to provide a lithium ion battery electrolyte, lithium ion battery and consumer, can solve under the high-pressure condition electrolyte composition to a certain extent and cause the problem of damage to the spinel structure of material easily to improve electrolyte and spinel structural electrode material's compatibility, simultaneously, and then guarantee the electrical property of 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 has a general structural formula shown in formula I:
wherein, R1-R4 are independently selected from one of hydrogen atom, fluorine substituted or unsubstituted C1-C6 chain alkyl, C3-C12 naphthenic base, C2-C6 alkylene or alkyne, C6-C12 alkylene, cyano, C1-C5 nitrile group, methoxy, ethoxy, phenyl, benzene ring derivative group and five-membered or six-membered heterocyclic group.
In the technical scheme, the electrolyte contains the additive components with the structural general formula, on one hand, the additive can participate in reaction through self open loop to form a stable SEI passivation protective film on the surfaces of a positive electrode and a negative electrode, so that HF generated by decomposition of the electrolyte components can be effectively prevented from corroding an electrode material with a spinel structure, and the effect of protecting the electrode material is achieved; on the other hand, the additive has weak alkaline N atoms, and the weak alkaline N atoms can neutralize partial HF generated in the electrolyte, so that the acidity of the electrolyte is reduced, and the additive also can play a role in protecting electrode materials. Through the synergistic effect of the two aspects, the additive can effectively prevent electrolyte components from damaging electrode materials under a high-voltage condition, so that the compatibility of the electrolyte and the electrode materials is improved, and the electrical performance of the battery is further ensured.
In some alternative embodiments, the additive comprises one or more of the following compound structures:
in the technical scheme, compared with other structures, the additive with the structural formula can better protect the electrode material.
In some optional embodiments, the additive in the electrolyte is 0.1 to 10% by mass;
optionally, the mass percentage of the additive in the electrolyte is 1-3%.
In the above technical scheme, the mass percent of the additive is limited to 0.1-10% because: if the dosage of the additive is too low, the electrode material cannot be well protected; if the amount of the additive is too large, resources are wasted because the additive remains in the electrolyte.
Furthermore, the mass percentage of the additive is limited to the range of 1-3%, so that the economic cost is lower under the condition of ensuring that the electrode material is well protected.
In some alternative embodiments, the lithium salt is present in the electrolyte in an amount of 10 to 20% by mass.
In the technical scheme, the dosage of the lithium salt is limited in the range, so that the lithium salt has a proper dosage ratio, and the charge and discharge performance of the battery is ensured.
In some alternative embodiments, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium difluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium difluorooxalate borate, lithium hexafluoroaluminate, lithium bistrifluoromethylsulfonylimide, lithium hexafluoroarsenate, and perfluoroalkyl sulfonylmethyllithium.
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.
In some alternative embodiments, the organic solvent comprises a fluorinated solvent;
optionally, the mass percentage of the fluorinated solvent in the organic solvent is 70 to 100%.
In the technical scheme, the fluorinated solvent is added in the organic solvent, and compared with the conventional organic solvent (the conventional solvent can be decomposed to generate gas under high pressure), the fluorinated solvent is stable under high pressure, so that the electrolyte is stable under high pressure.
Further, limiting the amount of the fluorinated solvent to the above range enables the fluorinated solvent to have an appropriate mass ratio in the organic solvent, thereby ensuring better high-pressure stability of the electrolyte.
In some alternative embodiments, the fluoro solvent comprises one or more of fluoroethylene carbonate, difluoroethylene carbonate, fluoropropylene carbonate, fluoroethyl carbonate, dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoroacetate, propyl fluoroacetate, ethyl fluoropropionate, and propyl fluoropropionate.
Among the above-mentioned technical scheme, the scheme of this application can be applicable to above-mentioned multiple fluoro solvent system better, provides more can the implementation scheme to be convenient for popularize and apply.
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 in the housing.
In the above technical solution, the lithium ion battery includes the lithium ion battery electrolyte provided in the embodiment of the first aspect, and damage to an electrode material caused by the electrolyte can be effectively avoided in a process of charging and discharging under a high-voltage condition, so that the electrical performance of the battery is ensured.
In some alternative embodiments, in the electrode assembly, the following conditions (a) and/or (b) are satisfied;
(a) Active materials for battery anodes include LiNi x Co y Mn z L (1-x-y-z) O 2 Wherein, L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1;
(b) The active material of the battery negative electrode includes one or more of graphite, soft carbon, hard carbon, silicon oxy-compound, and silicon-carbon composite.
In the technical scheme, the scheme of the application can be well suitable for the active material systems of the anodes of the various batteries and the active material system of the cathode of the battery, 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 carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
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, the lithium salt in the lithium ion battery electrolyte usually contains lithium hexafluorophosphate (LiPF) 6 ) The electrolyte can be decomposed into HF under high pressure, the HF can damage the structure of the spinel-structured electrode material, and in addition, the organic solvent in the electrolyte can also be decomposed into gas under high pressure, so that the electrical performance of a battery with the electrode material is influenced.
Based on this, the inventors have provided an electrolyte containing an additive having a specific structure, wherein the additive in the electrolyte can form an SEI passivation protective film on the surface of an electrode, and at the same time, can neutralize a part of HF in the electrolyte, thereby functioning to protect the electrode material.
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 a lithium ion battery electrolyte, including an organic solvent, a lithium salt, and an additive, where the additive has a general structural formula shown in formula I:
wherein, R1-R4 are independently selected from one of hydrogen atom, fluorine substituted or unsubstituted C1-C6 chain alkyl, C3-C12 naphthenic base, C2-C6 alkylene or alkyne, C6-C12 cycloolefine, cyano, C1-C5 nitrile group, methoxy, ethoxy, phenyl, benzene ring derivative group and five-membered or six-membered heterocyclic group.
In the application, the electrolyte contains the additive components with the structural general formula, on one hand, the additive can participate in reaction through self open loop to form a stable SEI passivation protective film on the surfaces of a positive electrode and a negative electrode, so that HF generated by decomposition of the electrolyte components can be effectively prevented from corroding electrode materials with a spinel structure, and the effect of protecting the electrode materials is achieved; on the other hand, the additive has weak alkaline N atoms, and the weak alkaline N atoms can neutralize partial HF generated in the electrolyte, so that the acidity of the electrolyte is reduced, and the additive also can play a role in protecting electrode materials. Through the synergistic effect of the two aspects, the additive can effectively prevent electrolyte components from damaging electrode materials under a high-voltage condition, so that the compatibility of the electrolyte and the electrode materials is improved, and the electrical performance of the battery is further ensured.
It should be noted that the structure of the additive is not limited, and can be adjusted according to actual needs.
As one example, the additive includes one or more of the following compound structures:
in this embodiment, the additive having the above structural formula can protect the electrode material better than other structures.
In other possible embodiments, the additive comprises one or more of the following compound structures:
it should be noted that the amount of the additive is not limited, and can be adjusted according to actual needs.
As an example, the mass percentage of the additive in the electrolyte is 0.1 to 10%, such as but not limited to 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10% or a range between any two.
Optionally, the mass percentage of the additive in the electrolyte is 1-3%, such as but not limited to any one of 1%, 1.5%, 2%, 2.5% and 3% or a range between any two.
In this embodiment, the reason why the mass percentage of the additive is limited to the range of 0.1 to 10% is that: if the dosage of the additive is too low, the electrode material cannot be well protected; if the amount of the additive is too large, resources are wasted due to the additive remaining in the electrolyte.
Furthermore, the mass percentage of the additive is limited to the range of 1-3%, so that the economic cost is lower under the condition of ensuring that the electrode material is well protected.
It should be noted that the amount of the lithium salt is not limited, and can be adjusted according to actual needs.
As an example, the mass percentage of the lithium salt in the electrolyte is 10 to 20%, such as but not limited to, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20% or a range between any two.
In this embodiment, the amount of the lithium salt is limited to the above range, so that the lithium salt can be used in an appropriate amount to ensure the charge and discharge performance of the battery.
It should be noted that the type of the lithium salt is not limited, and can be adjusted according to actual needs.
As one example, the lithium salt includes one or more of lithium hexafluorophosphate, lithium perchlorate, lithium difluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium difluorooxalate borate, lithium hexafluoroaluminate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, and perfluoroalkyl sulfonyl methyllithium.
In the embodiment, 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.
Since the conventional organic solvent is difficult to stably exist under high pressure conditions, the composition of the organic solvent in the electrolytic solution can be adjusted in consideration of the overall stability of the electrolytic solution.
As one example, the organic solvent includes a fluorinated solvent;
optionally, the mass percent of the fluorinated solvent in the organic solvent is 70-100%.
In this embodiment, the organic solvent is added with the fluorinated solvent, and the fluorinated solvent is stable under high pressure, so that the electrolyte is stable under high pressure, compared with the conventional organic solvent (which decomposes and generates gas under high pressure).
Further, limiting the amount of the fluorinated solvent to the above range enables the fluorinated solvent to have an appropriate mass ratio in the organic solvent, thereby ensuring better high-pressure stability of the electrolyte.
It should be noted that the kind of the fluorinated solvent is not limited, and may be adjusted according to actual needs.
As an example, the fluoro solvent includes one or more of fluoroethylene carbonate, difluoroethylene carbonate, fluoropropylene carbonate, fluoroethyl carbonate, dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoroacetate, propyl fluoroacetate, ethyl fluoropropionate, and propyl fluoropropionate.
In this embodiment, the scheme of the present application can be well applied to the above-mentioned various fluorinated solvent systems, and more practical schemes are provided, thereby facilitating popularization and application.
It is to be understood that the kind of the common solvent among the organic solvents is not limited.
As an example, common solvents include one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, propyl acetate, ethyl propionate, and propyl propionate.
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 in the housing.
In this embodiment, the lithium ion battery includes the lithium ion battery electrolyte provided in the embodiment of the first aspect, and damage to an electrode material caused by the electrolyte can be effectively avoided in a process of performing charge and discharge under a high-voltage condition, so that the electrical performance of the battery is ensured.
As an example, in the electrode assembly, the following conditions (a) and/or (b) are satisfied;
(a) Active materials for battery anodes include LiNi x Co y Mn z L (1-x-y-z) O 2 Wherein, L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1;
(b) The active material of the battery negative electrode includes one or more of graphite, soft carbon, hard carbon, silicon oxy-compound and silicon carbon composite.
In this embodiment, the scheme of the application can be better applied to the active material systems of the above-mentioned various battery anodes and the active material system of the battery cathode, and more implementable 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.
It should be noted that 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:
mixing common organic solvent and fluoro solvent; among the common organic solvents are: 7.5% Ethylene Carbonate (EC) and 7.5% Ethyl Methyl Carbonate (EMC); the fluorinated solvent includes: 64.5% fluoroethyl methyl carbonate (FEMC) and 5% fluoroethylene carbonate (FEC).
To the mixed solvent were added 0.5% of compound 1 and 15% of lithium hexafluorophosphate (LiPF) 6 ) And uniformly mixing to obtain the lithium ion battery electrolyte.
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: to the mixed solvent was added 1% of compound 1, and the change in the mass of the compound was adjusted by the amount of fluoroethyl carbonate (FEMC).
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: to the mixed solvent was added 2% of compound 1, and the change in the mass of the compound was adjusted by the amount of fluoroethyl carbonate (FEMC).
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: to the mixed solvent was added 3% of compound 1, and the change in the mass of the compound was adjusted by the amount of fluoroethyl carbonate (FEMC).
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: to the mixed solvent was added 5% of compound 1, and the change in the mass of the compound was adjusted by the amount of fluoroethyl carbonate (FEMC).
Example 6
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent was added 2% of compound 2.
Example 7
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent was added 2% of compound 3.
Example 8
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent was added 2% of compound 4.
Example 9
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent, 1% of compound 1 and 1% of compound 2 were added.
Example 10
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent, 1% of compound 1 and 1% of compound 3 were added.
Example 11
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 3 in that: to the mixed solvent, 1% of compound 1 and 1% of compound 4 were added.
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 solvent, 1% of compound 1, 1% of compound 2 and 1% of compound 4 were added.
Example 13
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: mixing a common organic solvent and a fluoro solvent; among the common organic solvents are: 6.5% Ethylene Carbonate (EC), 6.5% Ethyl Methyl Carbonate (EMC) and 2% diethyl carbonate (DEC); the fluorinated solvent includes: 64.5% fluoroethyl methyl carbonate (FEMC) and 5% diethyl Fluorocarbonate (FDEC).
Example 14
The embodiment of the application provides a preparation method of a lithium ion battery electrolyte, which is different from the embodiment 1 in that: mixing only common organic solvents; among the common organic solvents are: 30.5% Ethylene Carbonate (EC), 30.5% Ethyl Methyl Carbonate (EMC) and 23.5% diethyl carbonate (DEC).
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: 0.5% of Compound 1 was not added to the mixed solvent, and the change in the mass of the compound was adjusted by the amount of fluoroethyl carbonate (FEMC).
Test example 1
Electrical Performance testing
The test method comprises the following steps:
the lithium ion battery electrolytes prepared in examples 1 to 14 and comparative example 1 were assembled into batteries and numbered correspondingly, and then the capacity retention rate of the battery was tested at 25 ℃ and 45 ℃ for 300 cycles, and the capacity retention rate, the capacity recovery rate and the thickness expansion rate of the battery were tested at 60 ℃ for 7 days.
Wherein the content of the first and second substances,
the assembly of the cell was carried out as follows:
s1 is measured as 96.8:2.0: liNi mixed at a mass ratio of 1.2 0.2 Co 0.2 Mn 0.2 Al 0.4 O 2 (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 95:1.5:1.5:2, mixing graphite (a negative active material), conductive carbon black (a conductive agent), styrene butadiene rubber and carboxymethyl cellulose (a binder) according to the mass ratio, and dispersing in deionized water to obtain negative 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, negative plate and ionic diaphragm (PE ceramic diaphragm with thickness of 20 microns) to prepare a bare cell, and assembling the bare cell, the shell and the lithium ion battery electrolyte prepared in the embodiments 1-14 and the comparative example 1 into a battery.
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 ℃ and cycle 300 weeks: and (3) placing the lithium ion battery at room temperature, then carrying out 300 charge-discharge cycles on the lithium ion battery under the current of 0.33C, testing the voltage window to be 3.0-4.9V, and recording the discharge retention capacity of the 300 th cycle.
Capacity retention test of the battery at 45 ℃ and 300 weeks cycling: and (3) placing the lithium ion battery in a constant temperature box at 45 ℃ for standing for 4h, then carrying out 300 charge-discharge cycles on the lithium ion battery under the current of 0.33 ℃, and recording the discharge retention capacity of the 300 th cycle, wherein the test voltage window is 3.0-4.9V.
Thickness swell ratio, capacity retention and capacity recovery test of the battery stored at 60 ℃ for 7 days: testing and recording the initial thickness and 0.33C discharge initial capacity of the lithium ion battery; and then charging the battery to 4.9V at constant current and constant voltage under the current of 0.33C, placing the battery in an explosion-proof oven at 60 ℃, testing the hot measurement thickness of the battery in the oven after storing for 7 days, taking out the battery, cooling the battery to room temperature, and testing the discharge retention capacity and recovery capacity of the battery when the battery is discharged to 3.0V at 0.33C.
The calculation formula is as follows:
capacity retention (%) at 300 cycles = (300-th discharge retention capacity/1-th cycle discharge capacity) × 100%;
storage capacity retention (%) = retention capacity/initial capacity × 100%;
capacity recovery (%) = recovery capacity/initial capacity × 100%;
thickness expansion (%) = (thickness measured thermally-initial thickness)/initial thickness × 100%.
TABLE 1 Electrical Property test results
Referring to table 1, from the results of the electrical property tests of examples 1 to 14 and comparative example 1, it can be seen that the capacity retention rate of the prepared battery at 25 ℃ and 45 ℃ for 300 weeks in a cycle and the capacity retention rate, the capacity recovery rate and the thickness expansion rate of the battery at 60 ℃ for 7 days are all significantly improved.
As can be seen from the results of the electrical characteristics tests of examples 1 to 5, when the mass percentage of the additive is in the range of 1% to 3%, 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 examples 3 and 6 to 12, and examples 4 and 12, it can be seen that the electrical properties can be improved approximately when the additive is used in a certain amount and the type of the additive is different.
From the results of the electrical properties tests of example 1 and example 13, it can be seen that the electrical properties can be improved approximately by changing the types of the common solvent and the fluorinated solvent when the amount of the fluorinated solvent is constant.
From the electrical property test results of example 1 and example 14, it can be seen that when the fluorinated solvent is added to the organic solution, the capacity retention rate of the prepared battery at 25 ℃ and 45 ℃ for 300 weeks in a cycle, and the capacity retention rate, the capacity recovery rate and the thickness expansion rate of the battery at 60 ℃ for 7 days are all significantly 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 (10)
1. The lithium ion battery electrolyte is characterized by comprising an organic solvent, a lithium salt and an additive, wherein the additive has a structural general formula shown in a formula I:
wherein, R1-R4 are independently selected from one of hydrogen atom, fluorine substituted or unsubstituted C1-C6 chain alkyl, C3-C12 naphthenic base, C2-C6 alkylene or alkyne, C6-C12 alkylene, cyano, C1-C5 nitrile group, methoxy, ethoxy, phenyl, benzene ring derivative group and five-membered or six-membered heterocyclic group.
2. The lithium ion battery electrolyte of claim 1 wherein the additive comprises one or more of the following compound structures:
3. the lithium ion battery electrolyte of claim 1, wherein the additive is present in the electrolyte in an amount of 0.1 to 10% by weight;
optionally, the additive in the electrolyte is 1 to 3% by mass.
4. The lithium ion battery electrolyte of any one of claims 1 to 3, wherein the mass percentage of the lithium salt in the electrolyte is 10 to 20%.
5. The lithium-ion battery electrolyte of claim 4, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium difluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium difluorooxalate borate, lithium hexafluoroaluminate, lithium bistrifluoromethylsulfonimide, lithium hexafluoroarsenate, and lithium perfluoroalkylsulfonylmethylate.
6. The lithium ion battery electrolyte of any of claims 1-3 wherein the organic solvent comprises a fluorinated solvent;
optionally, the mass percentage of the fluorinated solvent in the organic solvent is 70 to 100%.
7. The lithium ion battery electrolyte of claim 6, wherein the fluorinated solvent comprises one or more of fluoroethylene carbonate, ethylene difluorocarbonate, propylene fluorocarbonate, ethyl methyl fluorocarbonate, dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoroacetate, propyl fluoroacetate, ethyl fluoropropionate, and propyl fluoropropionate.
8. A lithium ion battery, comprising:
a housing;
an electrode assembly housed within the case; and
the lithium ion battery electrolyte of any of claims 1-7 contained within the housing.
9. The lithium ion battery according to claim 8, wherein in the electrode assembly, the following conditions (a) and/or (b) are satisfied;
(a) Active materials for battery anodes include LiNi x Co y Mn z L (1-x-y-z) O 2 Wherein, L is one or more of Al, sr, mg, ti, ca, zr, zn, si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1;
(b) The active material of the battery negative electrode includes one or more of graphite, soft carbon, hard carbon, silicon oxy-compound, and silicon-carbon composite.
10. An electrical consumer, characterized in that the electrical consumer comprises a lithium ion battery according to claim 8 or 9.
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