CN113948771A - Safe low-concentration electrolyte for lithium battery and application thereof - Google Patents
Safe low-concentration electrolyte for lithium battery and application thereof Download PDFInfo
- Publication number
- CN113948771A CN113948771A CN202111200889.4A CN202111200889A CN113948771A CN 113948771 A CN113948771 A CN 113948771A CN 202111200889 A CN202111200889 A CN 202111200889A CN 113948771 A CN113948771 A CN 113948771A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- concentration
- solvent
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 97
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 87
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 87
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 239000006184 cosolvent Substances 0.000 claims abstract description 37
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- PGRMNXHYAZYNPG-UHFFFAOYSA-N fluoro hydrogen carbonate Chemical compound OC(=O)OF PGRMNXHYAZYNPG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VNXYDFNVQBICRO-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methoxypropane Chemical compound COC(C(F)(F)F)C(F)(F)F VNXYDFNVQBICRO-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- IESBVSNCDNHMSL-UHFFFAOYSA-N 2-[bis(2,2,2-trifluoroethoxy)methoxy]-1,1,1-trifluoroethane Chemical compound FC(F)(F)COC(OCC(F)(F)F)OCC(F)(F)F IESBVSNCDNHMSL-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- KGPPDNUWZNWPSI-UHFFFAOYSA-N flurotyl Chemical compound FC(F)(F)COCC(F)(F)F KGPPDNUWZNWPSI-UHFFFAOYSA-N 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- ZDCRNXMZSKCKRF-UHFFFAOYSA-N tert-butyl 4-(4-bromoanilino)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1NC1=CC=C(Br)C=C1 ZDCRNXMZSKCKRF-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 229910013075 LiBF Inorganic materials 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007793 non-solvation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Images
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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/056—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
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a safe low-concentration electrolyte for a lithium battery and application thereof, belonging to the field of secondary batteries. The electrolyte contains lithium salt, a solvent for dissolving the lithium salt and a non-solvating cosolvent, wherein the lithium salt is a mixed lithium salt rich in fluorine elements, the concentration of the whole lithium salt is not more than 0.6mol/L, the solvent is a single or mixed solvent, and the cosolvent is a fluorinated solvent. The invention overcomes the problem that the low-concentration electrolyte in the prior art cannot give consideration to high performance and high safety, realizes the low-concentration electrolyte which can make the lithium battery stably circulate and be safe by reasonably designing the components of the lithium salt, the solvent and the cosolvent, has lower lithium salt concentration compared with the traditional electrolyte, can obviously reduce the cost of the electrolyte, and finally obtains the electrolyte for the lithium battery with low cost, high performance and high safety.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a safe low-concentration electrolyte for a lithium battery and application thereof.
Background
Metallic lithium has the highest theoretical specific capacity (3860mAh/g) and the lowest redox potential (-3.04V vs. standard hydrogen electrode), so a lithium metal battery using metallic lithium directly as a negative electrode is considered as a next-generation high energy density battery. However, large scale application of lithium metal batteries presents serious challenges, on the one hand, non-uniform deposition and unstable interface of the lithium negative electrode during cycling can lead to rapid decay of the negative electrode capacity and potential safety issues, and on the other hand, destruction of the positive electrode structure can lead to loss of active material and failure of the battery.
The electrolyte is contacted with the positive electrode and the negative electrode simultaneously, is regarded as the blood of the battery, and can obviously improve the cycle life and the safety of the lithium metal battery. In order to realize a high-performance and high-safety lithium metal battery, researchers developed a series of novel electrolytes, and as found by zhangguang et al in the laboratories of north western countries of pacific usa, the high-concentration electrolytes can significantly improve the performance of the lithium metal battery and can improve the safety of the battery (nat. commun.2015, 6, 6362). However, the high concentration of the electrolyte increases the cost and viscosity of the electrolyte, and decreases wettability and conductivity. From the viewpoint of cost, researchers developed a new type of low concentration electrolyte (adv. energy mater.2020, 10,2001440). However, low concentration electrolytes contain a large number of free solvent molecules, are extremely flammable, and can pose a serious safety hazard when used.
Therefore, in order to realize the practical application of the lithium metal battery, it is increasingly important to develop a low-concentration electrolyte with low cost, high performance and high safety.
Through retrieval, the Chinese patent application number: 2019111920541, the name of invention creation is: a diluted lithium mixed lithium salt electrolyte for a lithium-sulfur battery comprises a mixed lithium salt, a solvent for dissolving the mixed lithium salt and a diluent, wherein the solvent for dissolving the mixed lithium salt is preferably an ester or ether solvent, and the diluent is preferably a fluoroether compound or an aromatic compound. The electrolyte can be used for a high-performance lithium-sulfur battery, and simultaneously plays a role in stabilizing a lithium negative electrode and promoting the performance of the capacity of a sulfur positive electrode. The electrolyte achieves the double effects of both lithium negative electrode protection and sulfur positive electrode capacity exertion by adding different lithium salts and mixing according to a certain proportion, and the electrolyte has high conductivity, low viscosity and good wettability due to the addition of the diluent, so that the cost of the electrolyte is greatly reduced, but the application does not relate to the inherent defects of the low-concentration electrolyte.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problem that the low-concentration electrolyte in the prior art cannot give consideration to high performance and high safety, and aims to provide the safe low-concentration electrolyte for the lithium battery and the application thereof.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a safe low-concentration electrolyte for a lithium battery, which comprises a lithium salt, a solvent for dissolving the lithium salt and a non-solvating cosolvent, wherein the lithium salt is a mixed lithium salt containing fluorine elements, the overall concentration of the lithium salt is not more than 0.6mol/L, the solvent is a single or mixed solvent, and the cosolvent is a fluoro solvent.
Further, the lithium salt is at least two of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonylimide, lithium bistrifluoromethylsulfonylimide, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluoroarsenate, lithium dioxalate borate, and lithium nitrate.
Furthermore, the concentration of the single lithium salt in the electrolyte is 0.1-0.3 mol/L, and the total concentration of the lithium salt is 0.2-0.6 mol/L.
Furthermore, the molar concentration ratio of the two selected lithium salts in the mixed lithium salt is (0.5-2) to 1.
Furthermore, the solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, fluoro carbonate, propylene carbonate, 1, 3-dioxolane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Further, the ratio of the solvent to the lithium salt is (1-10) to 1.
Further, the co-solvent is at least one of 1, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether, 2, 2, 2-trifluoroethyl ether, tris (trifluoroethoxy) methane, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methyl ether, 1H, 5H-octafluoropentyl-1, 1, 2, 2-tetrafluoroethyl ether, and 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether.
Further, the ratio of the amounts of the co-solvent and the lithium salt is (1-10): 1.
Further, the mass ratio of the co-solvent to the solvent is (1-10): 1.
According to the application of the low-concentration electrolyte for the safe lithium battery, the negative electrode material of the applied lithium battery is metal lithium or copper foil, and the positive electrode material is one or more of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, lithium nickelate, nickel-cobalt-manganese ternary, nickel-cobalt-aluminum ternary, sulfur, oxygen, carbon dioxide and air; the diaphragm of the lithium battery is a polypropylene diaphragm, a polyethylene diaphragm, a composite diaphragm of polypropylene and polyethylene, and Al2O3A coated membrane, a glass fiber membrane, a polytetrafluoroethylene membrane, a cellulose membrane or an aramid membrane.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) according to the low-concentration electrolyte disclosed by the invention, the mixed lithium salt rich in fluorine is selected to replace a traditional single lithium salt system, so that the solvation structure of the electrolyte can be adjusted, a stable interface can be formed at a positive electrode and a negative electrode, the cycle stability of a lithium negative electrode and the structural stability of the positive electrode are improved, and the action effect of '1 +1 > 2' is obtained.
(2) According to the low-concentration electrolyte, the non-solvation fluoro cosolvent is added into a traditional electrolyte solvent system, so that the interaction between lithium salt and a solvent can be enhanced, and the molecular weight of a free solvent is remarkably reduced, so that a solvation structure similar to that in a high-concentration electrolyte is realized under the condition of the low-concentration electrolyte, the safety of the electrolyte can be further improved, and the flame retardant effect is achieved.
(3) The low-concentration electrolyte can be applied to next-generation high-energy-density lithium metal batteries, the negative electrode of the lithium metal battery is metal lithium or copper foil, the positive electrode material is one or more of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, lithium nickelate, nickel-cobalt-manganese ternary, nickel-cobalt-aluminum ternary, sulfur, oxygen, carbon dioxide and air, and the electrolyte has the advantages of low cost, high performance and high safety, and has extremely high commercial prospect.
Drawings
Fig. 1 is a schematic diagram of the coulombic efficiency test of example 1 on a lithium negative electrode using a general low-concentration electrolyte and a low-concentration electrolyte with a co-solvent added.
Fig. 2 is a schematic of the coulombic efficiency test for lithium negative electrodes of example 2 using electrolytes of different concentrations.
Fig. 3 is a schematic of the coulombic efficiency test for a lithium negative electrode of example 3 using single lithium salt and mixed lithium salt electrolytes.
Fig. 4 is a schematic of the coulombic efficiency test for the lithium negative electrode of example 4 using different kinds of mixed lithium salt electrolytes.
Fig. 5 is a schematic of the coulombic efficiency test for the lithium negative electrode of example 5 using different concentrations of the mixed lithium salt electrolyte.
Fig. 6 is a schematic diagram of the first turn charge-discharge curves of the Li-622 battery assembled in example 6 using electrolytes of different concentrations.
Fig. 7 is a schematic diagram of the first charge-discharge curves of the Li-LCO battery assembled from low-concentration electrolytes of example 7 using different solvents.
Fig. 8 is a schematic of the cycling curve for a Li-LCO cell assembled in example 8 using the low concentration electrolyte proposed by the present invention.
FIG. 9 is a schematic diagram of the deposition profile of lithium metal in example 9 using the low concentration electrolyte of the present invention.
FIG. 10 is a graph showing the safety test of example 10 using the low concentration electrolyte according to the present invention.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The invention relates to a low-concentration electrolyte for a lithium battery, which comprises a lithium salt, a solvent for dissolving the lithium salt and a non-solvating cosolvent, wherein the lithium salt is a mixed lithium salt rich in fluorine elements, the concentration of the whole lithium salt is not more than 0.6mol/L, the solvent is a single or mixed solvent, and the cosolvent is a fluorinated solvent.
The lithium salt in the present invention is at least two of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonylimide, lithium bistrifluoromethylsulfonylimide, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluoroarsenate, lithium dioxalate borate and lithium nitrate, and in the examples, the description is not repeated one by one, and lithium difluorooxalato borate and lithium tetrafluoroborate are more preferable; the concentration of the single lithium salt in the electrolyte is 0.1 mol/L-0.3 mol/L, and the total concentration of the lithium salt is 0.2 mol/L-0.6 mol/L, which are not enumerated in the examples, and more preferably, the concentration of the single lithium salt is 0.3mol/L, and the total concentration of the lithium salt is 0.6 mol/L.
The molar concentration ratio of the two selected mixed lithium salts is (0.5-2) to 1, and in the embodiment, the two mixed lithium salts are not enumerated one by one, and the preferred ratio is 1: 1; the solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, fluoro carbonate, propylene carbonate, 1, 3-dioxolane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, which are not enumerated in the examples one by one, and fluoro carbonate is more preferable; the ratio of the amount of the solvent to the amount of the lithium salt is (1-10): 1, in the examples, no more than one is enumerated, and further, 10: 1 is preferable.
The cosolvent is at least one of 1, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether, 2, 2, 2-trifluoroethyl ether, tris (trifluoroethoxy) methane, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methyl ether, 1H, 5H-octafluoropentyl-1, 1, 2, 2-tetrafluoroethyl ether, and 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, which is not specifically enumerated in the examples, and is more preferably 1, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether; the ratio of the amounts of the co-solvent and the lithium salt is (1-10): 1, in the examples, the following are not enumerated one by one, and more preferably 10: 1; the mass ratio of the cosolvent to the solvent is (1-10): 1, in the examples, the following are not enumerated one by one, and more preferably 1: 1.
the present invention will be further described with reference to the following examples.
Example 1
Respectively preparing co-solvent-free lithium salt with concentration of 0.6M (specifically 0.3M LiDFOB +0.3M LiBF)4In FEC solvent) and 06M additive cosolvent (specifically 0.3M LiDFOB +0.3M LiBF)4Dissolving in mixed solvent of FEC/TTE, the volume ratio of FEC to TTE is 1: 1), assembling the electrolyte with a lithium sheet, a copper sheet and a diaphragm to form a lithium-copper half cell, and performing electrochemical plating at 1mA cm-2The coulombic efficiency test was performed at the current density of (1), as shown in fig. 1, the average coulombic efficiency of the lithium negative electrode was less than 90% in the 0.6M co-solvent-free control group, while the average coulombic efficiency of the lithium negative electrode was close to 100% in the 0.6M co-solvent-added experimental group. This example shows that the addition of a co-solvent has a significant effect on the properties of the low-concentration electrolyte.
Example 2
Respectively preparing a co-solvent-free lithium salt with the concentration of 1M (specifically 0.5M LiDFOB +0.5M LiBF)4In FEC solvent), 2M co-solvent free (specifically 1M LiDFOB +1M LiBF)4Dissolved in the solvent for FEC) and 0.6M additive co-solvent (specifically 0.3M LiDFOB +0.3M LiBF)4Dissolving FEC/TTE in solvent, wherein the volume ratio of FEC to TTE is 1: 1), assembling the electrolyte with a lithium sheet, a copper sheet and a diaphragm to form a lithium-copper half cell, and performing electrochemical machining (electrochemical) electrochemical machining (electrochemical) and/electrochemical machining (-2The coulombic efficiency test was performed at the current density of (1M) no-cosolvent control group, as shown in fig. 2, and the performance of the experimental group with the cosolvent added at 0.6M and the control group with no cosolvent at 2M was similar, and the lithium negative electrode was stably cycled. This example shows that by adding a co-solvent to a low-concentration electrolyte, excellent properties similar to those of a high-concentration electrolyte can be obtained.
Example 3
Respectively preparing single lithium salt (specifically 0.6M LiBF) with lithium salt concentration4Dissolving in FEC/TTE solvent at a volume ratio of FEC to TTE of 1: 1) and mixed lithium salt (specifically 0.3M LiDFOB +0.3M LiBF)4Dissolving in FEC/TTE solvent, the volume ratio of FEC and TTE is 1: 1), assembling into lithium-copper half-cell together with lithium sheet, copper sheet and diaphragm at 1mA cm-2The coulombic efficiency test was performed at the current density of (1), as shown in fig. 3, in the single lithium salt control group, the coulombic efficiency of the lithium negative electrode gradually decreased, while in the mixed lithium saltIn the experimental group, the coulombic efficiency of the lithium negative electrode can be kept stable. This example shows that the use of a mixed lithium salt in a low concentration electrolyte has superior performance to a single lithium salt.
Example 4
Respectively preparing low-concentration electrolyte composed of different lithium salts, assembling the electrolyte, a lithium sheet, a copper sheet and a diaphragm into a lithium-copper half cell together, and packaging at 1mA em-2The coulombic efficiency test was carried out at the current density of (1), as shown in fig. 4, in the case where the lithium salt composition was liddob + LiBF4The coulombic efficiency of the lithium negative electrode is highest, and the negative electrode stability is the last. This example shows that the optimum combination of using this mixed lithium salt in a low concentration electrolyte is LiDFOB + LiBF4。
Example 5
Respectively preparing different lithium salts (the selected lithium salts are LiDFOB and LiBF)4The solvent is a mixed solvent of FEC/TTE, the volume ratio of FEC to TTE is 1: 1) concentration mixed lithium salt low-concentration electrolyte comprises 0.1M +0.1M, 0.1M +0.2M, 0.2M +0.2M, 0.2M +0.3M and 0.3M +0.3M, the electrolyte, a lithium sheet, a copper sheet and a diaphragm are assembled together to form the lithium-copper half cell, and the lithium-copper half cell is assembled at 1mA cm-2The coulombic efficiency test was performed at the current density of (1), as shown in fig. 5, the low concentration electrolyte having the mixed lithium salt concentration of 0.3M +0.3M had the most excellent lithium negative electrode stability. This example shows that the optimum ratio for using the mixed lithium salt in a low concentration electrolyte is 0.3M + 0.3M.
Example 6
Respectively preparing low-concentration co-solvent-free (specifically 0.3M LiDFOB +0.3M LiBF)4In FEC solvent), high concentration co-solvent free (specifically 0.6M lidfo +0.6M LiBF)4Dissolved in FEC solvent) and low concentration co-solvent (specifically 0.3M LiDFOB +0.3M LiBF)4Dissolving the electrolyte in a FEC/TTE solvent, wherein the volume ratio of FEC to TTE is 1: 1), assembling the electrolyte, a lithium sheet, a 622 positive plate and a diaphragm into a Li-622 battery, and carrying out charging and discharging tests on the Li-622 battery. The first cycle of charge and discharge curves are shown in fig. 6, and the results show that the Li-622 using the low-concentration co-solvent-free control group can not be normally charged and discharged and has larger polarization. And high concentrations are free of co-solvents andthe electrolyte with low concentration of cosolvent can be normally circulated, and the polarization phenomenon is very small. This example shows that by adding a co-solvent to a low concentration electrolyte, excellent performance similar to that of a high concentration electrolyte can be obtained, all enabling stable cycling of a lithium metal full cell.
Example 7
Respectively preparing low-concentration electrolyte with DEC and FEC as solvents, wherein lithium salt is 0.3M LiDFOB +0.3M LiBF4The electrolyte, the lithium sheet, the LCO positive plate and the diaphragm are assembled together to form the Li-LCO battery, and the Li-LCO battery is subjected to charge and discharge tests. The first cycle of charge and discharge curves are shown in fig. 7, and the results show that the electrolyte with a low concentration of DEC as a solvent has a large polarization. And the polarization of the electrolyte with low concentration using FEC as solvent is very small. This example shows that the use of FEC as a solvent in a low-concentration electrolyte has superior performance.
Example 8
Configuration of 0.3M LiDFOB +0.3M LiBF4A Li-LCO battery was assembled using a low-concentration electrolyte solution dissolved in FEC/TTE (v/v ═ 1) together with a lithium plate, an LCO positive plate, and a separator, and subjected to a charge/discharge test. The cycling curve is shown in fig. 8, the charging and discharging interval is 3-4.6V, and the result shows that even if the charge cut-off voltage is as high as 4.6V, the Li-LCO battery assembled by the low-concentration electrolyte experimental group can still stably cycle, and almost has no capacity fading. This example shows that the low concentration electrolyte proposed by the present invention has excellent performance when used in a lithium metal battery.
Example 9
Configuration of 0.3M LiDFOB +0.3M LiBF4Low concentration electrolyte dissolved in FEC/TTE (v/v ═ 1), and lithium copper half-cell assembled by using the electrolyte together with lithium sheet, copper sheet and diaphragm, 3mAh em was deposited-2The lithium is on the surface of the copper sheet, the copper sheet is taken out to shoot the appearance of the lithium deposition, and as shown in fig. 9, the lithium deposited by the electrolyte has a uniform and compact surface. This example shows that the low concentration electrolyte proposed by the present invention can achieve dense lithium deposition.
Example 10
Configuration of 0.3M LiDFOB +0.3M LiBF4Dissolved in FEC-The test results of a low concentration electrolyte of TTE (v/v ═ 1) soaked in a common paper towel are shown in fig. 10, and the paper towel soaked with the low concentration electrolyte can not be ignited by fire, which shows that the paper towel has good flame retardancy. This example shows that the low concentration electrolyte proposed by the present invention has excellent safety.
Example 11
The low concentration electrolyte for lithium battery of this example, the selection of lithium salt, solvent and co-solvent is basically the same as example 1, except that the single lithium salt concentration of the two mixed lithium salts in this example is 0.1mol/L, and the total lithium salt concentration is 0.2 mol/L; the ratio of the amount of solvent to the amount of lithium salt mixture is 5: 1, and the ratio of the amount of co-solvent to the amount of lithium salt mixture is 10: 1.
Example 12
The low concentration electrolyte for lithium battery of this example, the selection of lithium salt, solvent and co-solvent is basically the same as example 1, except that the single lithium salt concentration of the two mixed lithium salts in this example is 0.2mol/L and 0.1mol/L, respectively, and the total lithium salt concentration is 0.3 mol/L; the ratio of the amount of solvent to the amount of lithium salt mixed material is 1: 1, and the ratio of the amount of co-solvent to the amount of lithium salt material is 10: 1.
Example 13
The low concentration electrolyte for a lithium battery of this example was substantially the same as example 1 in selecting the lithium salt, solvent and co-solvent, except that the amount ratio of the solvent to the substance mixing the lithium salt was 2: 1 and the amount ratio of the co-solvent to the substance mixing the lithium salt was 8: 1.
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (10)
1. A safe low-concentration electrolyte for a lithium battery is characterized in that: the lithium salt is a mixed lithium salt containing fluorine elements, the overall concentration of the lithium salt is not more than 0.6mol/L, the solvent is a single or mixed solvent, and the cosolvent is a fluorinated solvent.
2. The low-concentration electrolyte for a safe lithium battery as claimed in claim 1, wherein: the lithium salt is at least two of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, lithium difluorophosphate, lithium hexafluoroarsenate, lithium dioxalate borate and lithium nitrate.
3. The low-concentration electrolyte for a safe lithium battery as claimed in claim 1, wherein: the concentration of single lithium salt in the electrolyte is 0.1-0.3 mol/L, and the total concentration of lithium salt is 0.2-0.6 mol/L.
4. The low-concentration electrolyte for a safe lithium battery as claimed in claim 1, wherein: the molar concentration ratio of two selected lithium salts in the mixed lithium salt is (0.5-2) to 1.
5. The low-concentration electrolyte for a safe lithium battery as claimed in claim 1, wherein: the solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, fluoro carbonate, propylene carbonate, 1, 3-dioxolane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
6. A safe low-concentration electrolyte for lithium battery as claimed in any one of claims 1 to 5, wherein: the ratio of the solvent to the lithium salt is (1-10) to 1.
7. The low-concentration electrolyte for a safe lithium battery as claimed in claim 1, wherein: the cosolvent is at least one of 1, 1, 2, 2-tetrafluoroethyl-2, 2, 3, 3-tetrafluoropropyl ether, 2, 2, 2-trifluoroethyl ether, tris (trifluoroethoxy) methane, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methyl ether, 1H, 5H-octafluoropentyl-1, 1, 2, 2-tetrafluoroethyl ether and 1, 1, 2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether.
8. A safe low-concentration electrolyte for lithium battery as claimed in any one of claims 1 to 5, wherein: the mass ratio of the cosolvent to the lithium salt is (1-10) to 1.
9. A safe low-concentration electrolyte for lithium battery as claimed in any one of claims 1 to 5, wherein: the mass ratio of the cosolvent to the solvent is (1-10) to 1.
10. The application of the safe low-concentration electrolyte for the lithium battery is characterized in that: the cathode material of the applied lithium battery is metal lithium or copper foil, and the anode material is one or more of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, lithium nickelate, nickel cobalt manganese ternary, nickel cobalt aluminum ternary, sulfur, oxygen, carbon dioxide and air; the diaphragm of the lithium battery is a polypropylene diaphragm, a polyethylene diaphragm, a composite diaphragm of polypropylene and polyethylene, and Al2O3A coated membrane, a glass fiber membrane, a polytetrafluoroethylene membrane, a cellulose membrane or an aramid membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200889.4A CN113948771A (en) | 2021-10-14 | 2021-10-14 | Safe low-concentration electrolyte for lithium battery and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200889.4A CN113948771A (en) | 2021-10-14 | 2021-10-14 | Safe low-concentration electrolyte for lithium battery and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113948771A true CN113948771A (en) | 2022-01-18 |
Family
ID=79329963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111200889.4A Pending CN113948771A (en) | 2021-10-14 | 2021-10-14 | Safe low-concentration electrolyte for lithium battery and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113948771A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114024036A (en) * | 2021-11-05 | 2022-02-08 | 中南大学 | Low-concentration lithium ion battery electrolyte and lithium ion battery prepared from same |
| CN114421014A (en) * | 2022-01-20 | 2022-04-29 | 中国科学技术大学 | Chlorinated ether electrolyte and application thereof |
| CN114512722A (en) * | 2022-03-09 | 2022-05-17 | 东莞理工学院 | Metal lithium-based secondary battery electrolyte and application thereof |
| CN114824489A (en) * | 2022-05-20 | 2022-07-29 | 武汉大学 | Medium-salt-concentration electrolyte for lithium-sulfur battery |
| CN115117453A (en) * | 2022-07-20 | 2022-09-27 | 武汉大学 | Electrolyte for lithium metal secondary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190123390A1 (en) * | 2017-10-19 | 2019-04-25 | Battelle Memorial Institute | Low flammability electrolytes for stable operation of lithium and sodium ion batteries |
| CN109935908A (en) * | 2019-04-02 | 2019-06-25 | 合肥工业大学 | Low concentration lithium salt electrolyte and lithium secondary battery comprising it |
| CN110911756A (en) * | 2019-11-28 | 2020-03-24 | 华中科技大学 | Diluted lithium salt mixed lithium-sulfur battery electrolyte |
| CN111276744A (en) * | 2020-02-12 | 2020-06-12 | 清华大学 | Local high-concentration lithium metal battery electrolyte containing anion receptor additive |
-
2021
- 2021-10-14 CN CN202111200889.4A patent/CN113948771A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190123390A1 (en) * | 2017-10-19 | 2019-04-25 | Battelle Memorial Institute | Low flammability electrolytes for stable operation of lithium and sodium ion batteries |
| CN109935908A (en) * | 2019-04-02 | 2019-06-25 | 合肥工业大学 | Low concentration lithium salt electrolyte and lithium secondary battery comprising it |
| CN110911756A (en) * | 2019-11-28 | 2020-03-24 | 华中科技大学 | Diluted lithium salt mixed lithium-sulfur battery electrolyte |
| CN111276744A (en) * | 2020-02-12 | 2020-06-12 | 清华大学 | Local high-concentration lithium metal battery electrolyte containing anion receptor additive |
Non-Patent Citations (1)
| Title |
|---|
| GEORGIOS NIKIFORIDIS ETAL.: "Low-Concentrated Lithium Hexafluorophosphate Ternary-based Electrolyte for a Reliable and Safe NMC/Graphite Lithium-Ion Battery", 《J.PHYS.CHEM.LETT》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114024036A (en) * | 2021-11-05 | 2022-02-08 | 中南大学 | Low-concentration lithium ion battery electrolyte and lithium ion battery prepared from same |
| CN114421014A (en) * | 2022-01-20 | 2022-04-29 | 中国科学技术大学 | Chlorinated ether electrolyte and application thereof |
| CN114512722A (en) * | 2022-03-09 | 2022-05-17 | 东莞理工学院 | Metal lithium-based secondary battery electrolyte and application thereof |
| CN114824489A (en) * | 2022-05-20 | 2022-07-29 | 武汉大学 | Medium-salt-concentration electrolyte for lithium-sulfur battery |
| CN115117453A (en) * | 2022-07-20 | 2022-09-27 | 武汉大学 | Electrolyte for lithium metal secondary battery |
| CN115117453B (en) * | 2022-07-20 | 2024-09-10 | 武汉大学 | Electrolyte for lithium metal secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113948771A (en) | Safe low-concentration electrolyte for lithium battery and application thereof | |
| CN109346767A (en) | A kind of solid polymer electrolyte and its application in lithium metal battery | |
| CN109546219A (en) | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte | |
| CN112133961B (en) | Gel electrolyte precursor and application thereof | |
| CN113013492B (en) | Organic electrolyte with wide working temperature area and sodium ion battery | |
| CN105870449B (en) | A kind of all solid state lithium-air battery composite positive pole and all solid state lithium-air battery | |
| CN109671982B (en) | High-temperature high-safety electrolyte matched with silicon-carbon negative electrode material for lithium ion battery | |
| CN113851721A (en) | Double-functional lithium metal battery electrolyte and application thereof | |
| US20220200047A1 (en) | Solid-liquid battery | |
| CN113113670A (en) | Non-combustible lithium metal battery electrolyte and preparation method thereof, lithium metal battery and preparation method thereof | |
| US10446826B2 (en) | Method for making lithium ionic energy storage element | |
| CN114204119A (en) | Lithium-sulfur battery electrolyte containing mixed lithium salt of low-polarity ethers | |
| CN110797544A (en) | High-performance lithium primary battery and preparation method thereof | |
| CN111640988A (en) | Lithium ion battery electrolyte based on perfluorosulfonyl vinyl ether and preparation method and application thereof | |
| CN106711495A (en) | Electrolyte for lithium battery | |
| CN113161609A (en) | Lithium-rich manganese-based high-voltage electrolyte and application thereof | |
| CN117855606A (en) | Lithium metal battery electrolyte containing biological micromolecular additive and preparation method thereof | |
| CN114447426B (en) | Lithium-sulfur battery electrolyte, preparation method thereof and lithium-sulfur battery | |
| US20230253620A1 (en) | Improved electrolyte for electrochemical cell | |
| KR20240046809A (en) | Low-temperature lithium-ion battery electrolyte and its manufacturing method and lithium-ion battery | |
| EP3861582B1 (en) | Improved rechargeable batteries and production thereof | |
| CN114927762A (en) | Fluorinated sulfonyl electrolyte, preparation method and application thereof, and lithium metal battery | |
| CN116031489A (en) | Lithium metal battery electrolyte and lithium metal battery thereof | |
| CN115312856A (en) | Non-combustion electrolyte of lithium battery and application thereof | |
| CN115020811A (en) | High-voltage electrolyte and lithium ion battery containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220118 |