CN111293359A - Additive for low-temperature lithium ion battery, electrolyte using additive and lithium ion battery - Google Patents
Additive for low-temperature lithium ion battery, electrolyte using additive and lithium ion battery Download PDFInfo
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- CN111293359A CN111293359A CN201910051863.4A CN201910051863A CN111293359A CN 111293359 A CN111293359 A CN 111293359A CN 201910051863 A CN201910051863 A CN 201910051863A CN 111293359 A CN111293359 A CN 111293359A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 106
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 76
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000654 additive Substances 0.000 title claims abstract description 69
- 230000000996 additive effect Effects 0.000 title claims abstract description 64
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000013183 functionalized metal-organic framework Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 53
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 37
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 34
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 34
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 22
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 14
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 claims description 9
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 5
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- DEIXAXKIKOHRED-UHFFFAOYSA-N 5-(4-chlorophenyl)-1,2-thiazole Chemical compound C1=CC(Cl)=CC=C1C1=CC=NS1 DEIXAXKIKOHRED-UHFFFAOYSA-N 0.000 claims description 2
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- 239000013132 MOF-5 Substances 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000013207 UiO-66 Substances 0.000 claims description 2
- 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 2
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000005501 phase interface Effects 0.000 abstract description 5
- 239000007790 solid phase Substances 0.000 abstract description 5
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000005303 weighing Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 10
- 239000013538 functional additive Substances 0.000 description 9
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910013188 LiBOB Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000004452 microanalysis Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- OEWVNDMERGAAKZ-UHFFFAOYSA-N C(O)(=O)F.C#C Chemical compound C(O)(=O)F.C#C OEWVNDMERGAAKZ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
-
- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention relates to an additive for a low-temperature lithium ion battery, and an electrolyte and a lithium ion battery using the additive. Wherein the additive is a functionalized metal-organic framework material. The electrolyte comprises an organic solvent, a composite lithium salt and an additive, wherein the organic solvent accounts for 80-89% by mass, the composite lithium salt accounts for 10-15% by mass, and the additive accounts for 0.1-10% by mass. The electrolyte can be used for a lithium ion battery, the stability of the lithium ion battery can be obviously improved, the conductivity, the dissociation degree and the solubility of the electrolyte at low temperature are improved, and Li is enhanced+Conduction rate, improvement of solid phase interface film of negative electrode of lithium ion batteryThe structure of (2) further reduces the low-temperature impedance of the battery and improves the high-rate performance of the battery. The method has simple and controllable steps and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of low-temperature electrolyte of lithium ion batteries, in particular to an additive for a low-temperature lithium ion battery, and electrolyte and a lithium ion battery using the additive.
Background
The electrolyte, which is used as a place for conducting energy carrier lithium ions between the positive and negative electrodes, is called "blood" of the lithium ion battery, and has a crucial influence on the life, safety, rate capability, and the like of the battery. However, when the lithium ion battery is used in winter or in severe cold areas, the battery can not provide enough electricity to cause the equipment to be unable to operate normally. The main factor causing the phenomenon lies in the narrow working temperature range of the electrolyte, and particularly, the conductivity of the electrolyte and the interface structure formed by the electrolyte and the anode and the cathode at low temperature almost have a decisive role on the low-temperature performance of the battery. The conventional improvement method is to add a certain amount of functional components such as film forming, flame retarding, overcharge resistance, etc. to the electrolyte as additives to improve the performance of the electrolyte. The electrolyte of the current commercial lithium ion battery generally adopts EC (ethylene carbonate) -based electrolyte, and the main component is LiPF (lithium ion Polymer)6(lithium hexafluorophosphate)/EC + DMC (other carbonate co-solvent). However, at low operating temperatures, such as-10 to-40 ℃, the selection of additives with specific functions while maintaining high rate performance of the battery remains a significant challenge in the field of lithium ion battery electrolytes.
The metal-organic framework Materials (MOFs) are coordination polymers which develop rapidly in the last decade, have three-dimensional pore structures, generally take metal ions as connecting points, and organic ligand sites support to form space 3D extension, are important novel porous materials except zeolite and carbon nanotubes, and are widely applied to catalysis, energy storage and separation. The MOFs have better application in the fields of catalysis, adsorption separation, identification and the like due to the adjustable structure. In recent years, the physical and chemical properties of the MOFs can be adjusted by functionalizing the MOFs through a post-modification method, so that the modified MOFs can be applied to more fields.
In the prior art, some reports have been made about low-temperature electrolyte materials, for example, CN102832409A discloses a low-temperature electrolyte for lithium ion batteries containing lithium borate-based electrolyte salt and a preparation method thereof; CN103413970A discloses a low-temperature lithium carbonate lithium battery electrolyte containing polydimethylsiloxane, 1, 3-propane sultone and vinylene carbonate additive; CN103500850B discloses a low-temperature electrolyte of a ternary nickel-cobalt-manganese material (NMC523) battery containing gamma-valerolactone (GVL), Vinylene Carbonate (VC), Ethylene Sulfite (ES) and Propylene Sulfite (PS) additives; CN101685880A discloses a preparation method of a low-temperature lithium ion battery electrolyte based on reduced pressure distillation impurity removal and molecular sieve/alkali metal adsorption dehydration; CN101645521A discloses a preparation method of a low-temperature functional electrolyte for lithium titanate lithium ion batteries.
Although the low-temperature electrolyte of the lithium battery is disclosed above, the application of MOFs in the lithium ion electrolyte to improve the rate capability of the lithium ion battery at low temperature has been reported in the prior art, and the main differences between the prior art and the present invention are as follows: 1. different additive materials, metal-organic framework Materials (MOFs) which do not exist in the prior art also exist in the present invention; 2. in contrast to the preparation methods, the present invention uses methods for functionalizing MOFs with other conventional additives. The material is an additive of a functionalized metal-organic framework material and application of low-temperature electrolyte containing the material in a lithium ion battery. MOFs in the material has the advantages of controllable pore size, large specific surface area and the like, and the structural stability of the additive can be obviously enhanced through the functionalization of the MOFs, the physical property of the electrolyte at low temperature is improved, and Li is enhanced+The conduction rate improves the structure of the solid phase interface film of the battery cathode, thereby improving the rate capability of the battery.
Based on the above, a low-temperature electrolyte for a lithium ion battery is expected, wherein the electrolyte contains an additive material of a functionalized metal-organic framework material, and MOFs can remarkably improve the stability of the electrolyte, improve the conductivity, the dissociation degree and the solubility of the electrolyte at low temperature and enhance Li+ConductionThe speed is improved, the structure of a cathode solid phase interface film of the lithium ion battery is improved, the low-temperature impedance of the lithium ion battery is further reduced, and the high-rate performance of the battery is improved.
Disclosure of Invention
The invention aims to provide an additive for a low-temperature lithium ion battery, and an electrolyte and the lithium ion battery using the additive. The additive material of the functionalized metal-organic framework material has the advantages of controllable aperture size, large specific surface area and the like, and when the additive material is applied to the electrolyte of a lithium ion battery, the battery has excellent low-temperature performance and high-rate performance, is low in cost and is suitable for industrial production.
The object of the present invention and the technical problem to be solved are achieved by the following technical means. The invention provides an additive for a low-temperature lithium ion battery, which is a functionalized metal-organic framework material.
The additive of the functionalized metal-organic framework material is selected from one or more of MOFs functionalized vinylene carbonate and derivatives thereof, MOFs functionalized fluoroethylene carbonate and derivatives thereof, MOFs functionalized gamma-valerolactone and derivatives thereof, MOFs functionalized ethylene sulfite and derivatives thereof, MOFs functionalized propylene sulfite and derivatives thereof, MOFs functionalized ethylene oxide and derivatives thereof, MOFs functionalized methacryloxyethyltrimethyl ammonium chloride or MOFs functionalized polyvinylpyrrolidone and derivatives thereof.
The MOFs mentioned above are selected from one or more of ZIF-67, ZIF-8, MOF-5, UIO-66, HKUST-1, and PCN-14.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the low-temperature electrolyte provided by the invention, the low-temperature electrolyte comprises an organic solvent, a composite lithium salt and the additive, wherein the organic solvent accounts for 80-89% by mass, the composite lithium salt accounts for 10-15% by mass, and the additive accounts for 0.1-10% by mass.
The content of the additive is 1.5-4%.
The organic solvent is one or more selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl acetate, N-methyl pyrrolidone, tetrahydrofuran and dimethyl ether.
The complex lithium salt is selected from one or more of lithium tetrafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate (V), lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethanesulfonate imide).
The purity of the organic solvent is more than 99.9 wt%, the water content is less than or equal to 30ppm, and the acidity is less than 50 ppm; the purity of the composite lithium salt is more than 99.9 wt%; the purity of the additive is >99.9 wt%.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The low-temperature lithium ion battery provided by the invention comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the low-temperature electrolyte.
By the technical scheme, the invention (name) at least has the following advantages:
(1) the claimed material is an additive for a functionalized metal-organic framework material, a low-temperature electrolyte containing the material and application of the low-temperature electrolyte in a low-temperature lithium ion battery. The MOFs in the additive has the advantages of controllable pore size, large specific surface area and the like, and the structural stability and the low-temperature performance of the additive can be remarkably enhanced by functionalizing the MOFs and the conventional additive.
(2) The invention also provides an electrolyte containing the functionalized metal-organic framework material additive, which not only retains the performance of the original electrolyte, but also fully shows the low-temperature performance of the additive, obviously improves the physical performance of the electrolyte at low temperature, enhances the Li < + > conduction rate and improves the structure of a solid phase interface film of a battery cathode.
(3) The invention also provides a low-temperature lithium ion battery, wherein the electrolyte is an additive of a functionalized metal-organic framework material, and the MOFs functionalized additive has a porous structure and a high specific surface area, so that the lithium ion battery can maintain excellent low-temperature performance and high-rate performance even under a low-temperature condition.
(4) Compared with the conventional lithium ion battery without the MOFs functionalized additive electrolyte, the lithium ion battery containing the MOFs functionalized additive electrolyte has obviously low battery impedance; the conductivity of the battery is higher at the normal temperature of 25 ℃ and the low temperature of-10 ℃, and at the temperature of-30 ℃ and-50 ℃, which shows that the electrolyte has good low-temperature conductivity and the conductivity is as high as 1.0 multiplied by 10 even at the temperature of-30 DEG C-3S/cm; the maximum discharge capacity can reach 84% of the battery capacity when the battery is discharged at the rate of 40C under normal temperature, and the large-rate discharge can be realized.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
The specific preparation method and structure of the present invention are given in detail by the following examples.
Drawings
FIG. 1 is a schematic view of the structure of an additive of MOFs-functionalized vinylene carbonate and its derivatives;
FIG. 2 is a schematic diagram of the structure of an additive of MOFs-functionalized vinylene fluorocarbonate and its derivatives;
FIG. 3 is a schematic diagram of the structure of an additive of MOFs functionalized gamma-valerolactone and derivatives thereof;
FIG. 4 is a schematic view of the structure of an additive of MOFs functionalized propylene sulfite and its derivatives;
FIG. 5 is a schematic view of the structure of an additive of MOFs-functionalized vinyl sulfite and its derivatives;
FIG. 6 is a schematic view of the structure of the additive of MOFs functionalized polyethylene oxides and their derivatives;
FIG. 7 is a schematic diagram of the structure of an additive of MOFs-functionalized methacryloyloxyethyl trimethylammonium chloride;
FIG. 8 is a schematic view of the structure of the additive of MOFs-functionalized polyvinylpyrrolidone and its derivatives;
FIG. 9 is an SEM representation of the MOFs-functional additive ZIF-8-VC in accordance with the present invention;
FIG. 10 is a TEM representation of the MOFs-functional additive ZIF-8-VC in accordance with the present invention;
FIG. 11 is a SEM representation of the MOFs functional additive UIO-66-GVL according to the present invention;
FIG. 12 is a TEM representation of the MOFs-functional additive UIO-66-GVL according to the present invention;
FIG. 13 is a graph comparing EIS test results of lithium ion batteries obtained in example 1, comparative example 1 and comparative example 2 according to the present invention at 25 ℃;
FIG. 14 is a graph comparing results of conductivity tests at different temperatures of electrolytes obtained in example 1, comparative example 1 and comparative example 2 according to the present invention;
fig. 15 shows the battery discharge curve performance of the low-temperature lithium ion battery obtained in example 1 according to the present invention at different rates;
fig. 16 shows the cell discharge curve performance of the low-temperature lithium ion battery obtained in example 1 of the present invention at different temperatures;
fig. 17 is a graph showing cell discharge curve performance at 10C and 20C of the lithium ion batteries obtained in example 1 according to the present invention and comparative example 1.
Detailed Description
The present invention is further illustrated by the following figures and examples, which are to be understood as merely illustrative and not restrictive. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
Example 1
Respectively weighing a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) in a mass ratio of 1: 4: 1 as a quaternary mixed organic solvent accounting for 85% of the total weight of the electrolyte in a glove box filled with high-purity argon by using a microanalysis balance, and collectingStir with magnetic force for 20 minutes. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB), accounting for 12% of the total weight of the electrolyte, adding the lithium bis (oxalato) borate into the quaternary mixed organic solvent, and stirring until the mixture is clear and free of precipitate. Weighing a certain amount of MOFs functionalized mixed additive ZIF-8-VC and UIO-66-GVL accounting for 3% of the total weight of the electrolyte, slowly adding the mixture into the solution, fully and uniformly stirring, standing for 2 hours, and then pouring the mixture into a sealed bottle to obtain 85% (PC-EC-DMC-MC)/12% (LiPF)4-LiBOB)/3% (ZIF-8-VC-UIO-66-GVL) low temperature electrolyte.
And a commercial ternary nickel-cobalt-manganese (NMC523) material is selected to be assembled by a conventional button cell process, and the low-temperature electrolyte is used as the electrolyte of the lithium ion battery to be assembled into the low-temperature lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained low-temperature lithium ion battery.
Example 2
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 85% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB), accounting for 12% of the total weight of the electrolyte, adding the lithium bis (oxalato) borate into the quaternary mixed organic solvent, and stirring until the mixture is clear and free of precipitate. Weighing a certain amount of MOFs functional additive ZIF-8-VC, which accounts for 3% of the total weight of the electrolyte. Slowly adding into the above solution, stirring, standing for 2 hr, and pouring into a sealed bottle to obtain 85% (PC-EC-DMC-MC)/12% (LiPF)4-LiBOB)/3% (ZIF-8-VC) low temperature electrolyte.
And a commercial ternary nickel-cobalt-manganese (NMC523) material is selected to be assembled by a conventional button cell process, and the low-temperature electrolyte is used as the electrolyte of the lithium ion battery to be assembled into the low-temperature lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained low-temperature lithium ion battery.
Example 3
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 85% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB), accounting for 12% of the total weight of the electrolyte. Adding the quaternary mixed organic solvent into the quaternary mixed organic solvent, and stirring until the quaternary mixed organic solvent is clear and has no precipitate. Weighing a certain amount of MOFs functionalized mixed additive ZIF-8-VC, UIO-66-GVL and HKUST-1-PS, wherein the weight of the mixed additive is 3% of the total weight of the electrolyte. Slowly adding into the above solution, stirring, standing for 2 hr, and pouring into a sealed bottle to obtain 85% (PC-EC-DMC-MC)/12% (LiPF)4-LiBOB)/3% (ZIF-8-VC-UIO-66-G VL-HKUST-1-PS) low temperature electrolyte.
And a commercial ternary nickel-cobalt-manganese (NMC523) material is selected to be assembled by a conventional button cell process, and the low-temperature electrolyte is used as the electrolyte of the lithium ion battery to be assembled into the low-temperature lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained low-temperature lithium ion battery.
Example 4
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 89% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB) accounting for 10.9 percent of the total weight of the electrolyte, adding the lithium bis (oxalato) borate into the quaternary mixed organic solvent, and stirring until the mixture is clear and has no precipitate. Weighing a certain amount of MOFs functionalized mixed additive ZIF-8-VC and UIO-66-GVL, wherein the mixed additive accounts for 0.1 percent of the total weight of the electrolyte. Slowly adding into the above solution, stirring, standing for 2 hr, and pouring into a sealed bottle to obtain 89% (PC-EC-DMC-MC)/10.9% (Li)PF4LiBOB)/0.1% (ZIF-8-VC-UIO-66-GVL) low temperature electrolyte.
And a commercial ternary nickel-cobalt-manganese (NMC523) material is selected to be assembled by a conventional button cell process, and the low-temperature electrolyte is used as the electrolyte of the lithium ion battery to be assembled into the low-temperature lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained low-temperature lithium ion battery.
Example 5
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 80% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB) in an amount of 10% by weight based on the total weight of the electrolyte. Adding the quaternary mixed organic solvent into the quaternary mixed organic solvent, and stirring until the quaternary mixed organic solvent is clear and has no precipitate. Weighing a certain amount of MOFs functionalized mixed additive ZIF-8-VC and UIO-66-GVL, wherein the mixed additive accounts for 10% of the total weight of the electrolyte. Slowly adding into the above solution, stirring, standing for 2 hr, and pouring into a sealed bottle to obtain 80% (PC-EC-DMC-MC)/10% (LiPF)4-LiBOB)/10% (ZIF-8-VC-UIO-66-GVL) low temperature electrolyte.
And a commercial ternary nickel-cobalt-manganese material (NMC523) is selected to be assembled by a conventional button cell process, and the low-temperature electrolyte is used as the electrolyte of the lithium ion battery to assemble the lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained lithium ion battery.
Comparative example 1
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 85% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And two grass of Japanese knotweedAnd adding acid lithium borate (LiBOB) accounting for 12% of the total weight of the electrolyte into the quaternary mixed organic solvent, and stirring until the solution is clear and has no precipitate. Weighing a certain amount of mixed additives of Vinylene Carbonate (VC) and gamma-valerolactone (GVL) which account for 3 percent of the total weight of the electrolyte, slowly adding the mixture into the solution, fully and uniformly stirring, standing for 2 hours, and then pouring the mixture into a sealed bottle to obtain 85 percent (PC-EC-DMC-MC)/12 percent (LiPF)4-LiBOB)/3% (VC-GVL) electrolyte.
And a commercial ternary nickel-cobalt-manganese material (NMC523) is selected to be assembled by a conventional button cell process, and the electrolyte is used as the electrolyte of the lithium ion battery to assemble the lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained lithium ion battery.
Comparative example 2
In a glove box filled with high-purity argon, a certain amount of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl acetate (MC) are respectively weighed by a microanalysis balance, the mass ratio of the Propylene Carbonate (PC), the Ethylene Carbonate (EC), the dimethyl carbonate (DMC) and the methyl acetate (MC) is 1: 4: 1, the propylene carbonate, the ethylene carbonate, the dimethyl carbonate and the methyl acetate are used as quaternary mixed organic solvents, the quaternary mixed organic solvents account for 85% of the. Weighing a certain amount of mixed lithium salt: lithium tetrafluorophosphate (LiPF)4) And lithium bis (oxalato) borate (LiBOB) accounting for 12% of the total weight of the electrolyte, adding the lithium bis (oxalato) borate into the quaternary mixed organic solvent, and stirring until the mixture is clear and free of precipitate. Weighing a certain amount of additive Vinylene Carbonate (VC) which accounts for 3 percent of the total weight of the electrolyte. Slowly adding into the above solution, stirring, standing for 2 hr, and pouring into a sealed bottle to obtain 85% (PC-EC-DMC-MC)/12% (LiPF)4-LiBOB)/3% VC electrolyte.
And a commercial ternary nickel-cobalt-manganese material (NMC523) is selected to be assembled by a conventional button cell process, and the electrolyte is used as the electrolyte of the lithium ion battery to assemble the lithium ion battery. And carrying out discharge capacity test and rate capability test at normal temperature and low temperature on the obtained lithium ion battery.
TABLE 1 comparison of discharge Capacity Properties at Normal and Low temperatures of lithium ion batteries in examples 1 to 5 and comparative examples 1 to 2
TABLE 2 comparison of the Rate Properties at Low temperatures of the lithium ion batteries in examples 1 to 5 and comparative examples 1 to 2
Table 1 is a comparison of discharge capacity performance at normal temperature and low temperature of the lithium ion batteries in examples 1 to 5 according to the present invention and comparative examples 1 to 2; table 2 shows a comparison of the rate performance at low temperature of the lithium ion batteries in examples 1 to 5 according to the present invention and comparative examples 1 to 2. As can be seen from Table 1, compared with the conventional electrolyte without MOFs functionalization, the electrolyte based on MOFs functionalization has higher discharge capacity performance at the normal temperature of 25 ℃ and the low temperature of-10 ℃, and at the temperature of-30 ℃ and-50 ℃, and shows that the electrolyte has good low-temperature electrolyte performance, wherein the reason is that Li in the electrolyte+The conduction rate is enhanced and the anode/electrolyte interface structure is improved. As can be seen from Table 2, compared with the conventional electrolyte without MOFs functionalization, the electrolyte based on MOFs functionalization of the invention has higher performances at 1C, 10C and 20C multiplying power at the low temperature of-30 ℃, and the electrolyte additive is proved to be more stable in structure. The results also show that the electrolyte can be used in a low-temperature high-rate lithium ion battery.
Other figures are illustrated below:
FIG. 9 is an SEM representation of the MOFs-functional additive ZIF-8-VC in accordance with the present invention; FIG. 10 is a TEM representation of the MOFs-functional additive ZIF-8-VC in accordance with the present invention. As can be seen in fig. 9, the MOFs functionalized additive ZIF-8-VC of the present invention has a hexadecahedron morphology, approximately 35 nm in size, consistent with the TEM image of fig. 10.
FIG. 11 is a SEM representation of the MOFs functional additive UIO-66-GVL according to the present invention; FIG. 12 is a TEM representation of the MOFs-functional additive UIO-66-GVL according to the present invention. As can be seen in FIG. 11, the morphology of the MOFs-functionalized additive UIO-66-GVL of the present invention is octahedral with a size of about 150 nm, consistent with the TEM image of FIG. 12.
Fig. 13 is a graph comparing EIS test results of the lithium ion batteries obtained in example 1 according to the present invention, comparative example 1 and comparative example 2 at 25 ℃. As can be seen from fig. 13, the cell impedances of example 1, comparative example 1 and comparative example 2 were about 85 Ω, 125 Ω and 165 Ω, respectively, and the results showed that the cell impedance in example 1 was significantly lower than those in comparative example 1 and comparative example 2.
Fig. 14 is a graph comparing results of conductivity tests at different temperatures of the electrolytes obtained in example 1, comparative example 1 and comparative example 2 according to the present invention. As can be seen from FIG. 14, the conductivity of the MOFs-based functionalized electrolyte of the present invention was higher at the normal temperature of 25 ℃ and at the low temperature of-10 ℃ and at the temperatures of-30 ℃ and-50 ℃ than that of the conventional electrolyte, indicating that the electrolyte has very good low-temperature conductivity and the conductivity thereof is as high as 1.0X 10 even at-30 DEG C-3S/cm。
Fig. 15 shows the cell discharge curve performance of the low-temperature lithium ion battery obtained in example 1 according to the present invention at different rates. As can be seen from fig. 15, the maximum discharge capacity of the battery at room temperature discharged at a rate of 40C can reach 84% of the battery capacity, indicating that the battery can realize large-rate discharge.
Fig. 16 shows the cell discharge curve performance of the low-temperature lithium ion battery obtained in example 1 of the present invention at different temperatures. As can be seen from FIG. 16, the capacity of the battery can still be kept at 67.3% at a low temperature of-30 ℃ and a cut-off voltage of 2.5V at 20C; at low temperature of-50 ℃, 20 ℃ and cut-off voltage of 2.0V, the capacity can still be maintained at 62.9 percent, and the low-temperature performance is good.
Fig. 17 is a graph showing cell discharge curve performance at 10C and 20C of the lithium ion batteries obtained in example 1 according to the present invention and comparative example 1. As can be seen from FIG. 17, the capacity of the battery can be maintained at 67.3% at a cut-off voltage of 2.5V at a low temperature of-30 ℃. The results of comparative example 1 and comparative example 2 show that the charging and discharging were not possible at 20C at a low temperature of-30 ℃ and the capacity of comparative example 1 was maintained at 34.1% at a low temperature of-30 ℃ and 10C at a cut-off voltage of 2.5V.
In conclusion, the low-temperature lithium ion battery adopts the functionalized metal-organic framework material additive, the MOFs functionalized additive has a porous structure and a high specific surface area, the physical performance of the electrolyte at low temperature is remarkably improved, the Li + conduction rate is enhanced, the structure of a battery cathode solid phase interface film is improved, and the lithium ion battery can also keep excellent low-temperature performance and high rate performance even under the low-temperature condition.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. An additive for low temperature lithium ion batteries, which is a functionalized metal-organic framework material.
2. The additive of claim 1, wherein the additive of the functionalized metal-organic framework material is selected from one or more of MOFs functionalized vinylene carbonate and its derivatives, MOFs functionalized fluoroethylene carbonate and its derivatives, MOFs functionalized gamma-valerolactone and its derivatives, MOFs functionalized vinyl sulfite and its derivatives, MOFs functionalized propylene sulfite and its derivatives, MOFs functionalized polyethylene oxide and its derivatives, MOFs functionalized methacryloxyethyltrimethyl ammonium chloride or MOFs functionalized polyvinylpyrrolidone and its derivatives.
3. Additive according to claim 1 or 2, wherein said MOFs are selected from one or more of ZIF-67, ZIF-8, MOF-5, UIO-66, HKUST-1, PCN-14.
4. A low-temperature electrolyte comprises an organic solvent, a composite lithium salt and the additive as claimed in any one of claims 1 to 3, wherein the content of the organic solvent is 80 to 89 percent by mass, the content of the composite lithium salt is 10 to 15 percent by mass, and the content of the additive is 0.1 to 10 percent by mass.
5. The low-temperature electrolyte as claimed in claim 4, wherein the additive is present in an amount of 1.5 to 4%.
6. The low-temperature electrolyte as claimed in claim 4, wherein the organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl acetate, N-methyl pyrrolidone, tetrahydrofuran, and dimethyl ether.
7. The cryogenic electrolyte of claim 4 wherein the complex lithium salt is selected from one or more of lithium tetrafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate (V), lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonyl) imide.
8. The cryogenic electrolyte of claim 4 wherein the organic solvent has a purity >99.9 wt%, a moisture content < 30ppm, an acidity <50 ppm; the purity of the composite lithium salt is more than 99.9 wt%; the purity of the additive is >99.9 wt%.
9. A low-temperature lithium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the low-temperature electrolyte as claimed in any one of claims 4 to 8.
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