CN114824481A - Electrolyte for high-voltage lithium metal battery and lithium metal battery - Google Patents
Electrolyte for high-voltage lithium metal battery and lithium metal battery Download PDFInfo
- Publication number
- CN114824481A CN114824481A CN202210517854.1A CN202210517854A CN114824481A CN 114824481 A CN114824481 A CN 114824481A CN 202210517854 A CN202210517854 A CN 202210517854A CN 114824481 A CN114824481 A CN 114824481A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- carbonate
- voltage
- battery
- 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 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 44
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 24
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 28
- 239000007774 positive electrode material Substances 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 8
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- BPCFDNSMCCXMDT-UHFFFAOYSA-N difluorophosphoryl dihydrogen phosphate Chemical compound OP(O)(=O)OP(F)(F)=O BPCFDNSMCCXMDT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011149 active material Substances 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 abstract description 7
- FNDXFUBHPXBGMD-UHFFFAOYSA-N OP(O)O.OP(O)(O)=O Chemical compound OP(O)O.OP(O)(O)=O FNDXFUBHPXBGMD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000011572 manganese Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 10
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IJSFJIZRDXMQIY-UHFFFAOYSA-N C[Si](C)(C)OP(OP(O[Si](C)(C)C)(F)=O)(F)=O Chemical compound C[Si](C)(C)OP(OP(O[Si](C)(C)C)(F)=O)(F)=O IJSFJIZRDXMQIY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VNWHJJCHHGPAEO-UHFFFAOYSA-N fluoroboronic acid Chemical compound OB(O)F VNWHJJCHHGPAEO-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- H01M10/056—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
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- 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
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
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 an electrolyte for a high-voltage lithium metal battery, which comprises lithium hexafluorophosphate, boron-containing lithium salt, a mixed solvent of organic solvent Hydrofluoroether (HFE) and cyclic carbonate and linear carbon ester, and an additive which is methyl silicon-based (phosphite) phosphate. Meanwhile, the lithium metal battery adopting the electrolyte is disclosed, wherein the anode adopts a lithium-manganese-rich or nickel-rich ternary active material and a lithium metal cathode. The electrolyte disclosed by the invention has a higher electrochemical window (>5V) due to the synergistic effect of the boron-containing lithium salt, the methyl silicon-based (phosphite) phosphate compound and the hydrofluoroether solvent in the electrolyte, and the battery shows good cycle stability and voltage stability due to the uniform and compact CEI film formed on the surface of the positive electrode of the battery.
Description
Technical Field
The present invention relates to a lithium metal battery and a key material thereof, and more particularly, to an electrolyte solution for a high voltage lithium metal battery and a lithium metal battery.
Background
With the continuous consumption of fossil energy, resources and environmental issues are receiving more and more attention. The development of clean, efficient and sustainable energy storage and conversion devices is an urgent problem to be solved. As a representative of new energy storage devices, lithium ion batteries have become a focus of research in various countries because of their advantages of high energy density, long cycle life, high output voltage, environmental friendliness, no memory effect, and the like.
The electrolyte is known as the 'blood' of the battery, and has important functions of carrying lithium ion transmission, generating a solid electrolyte membrane on the interface of a positive electrode and a negative electrode and the like in the battery. Because trace moisture is inevitably introduced in the manufacturing process of each part of the battery core, free HF may exist in the electrolyte due to lithium salt, and in addition, part of the lithium salt is sensitive to water, especially LiPF commonly used at present 6 Easily react with water to form POF 3 Strong lewis acids such as HF. The strong lewis acid generated in these reactions decomposes carbonate solvents such as Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) on the electrode surface to form lithium carbonate (Li) 2 CO 3 ) Products such as lithium alkyl salt (ROCOOLi), lithium fluoride (LiF) and the like cover the surface of the electrode material, so that the interface impedance of the electrode/electrolyte is increased, and the cycle rate performance of the battery is influenced. Meanwhile, the formed HF can continuously erode the anode material and react with the transition metal ions in a high oxidation state to cause the transition metal to be dissolved, and even cause the structure of the anode material to be subjected to irreversible transformation; in addition, the anode material is easy to have violent structural transformation under high pressure, and the traditional carbonate-based electrolyte has lower oxidative decomposition potential and is oxidized and decomposed under high pressure of more than 4.5VThe reaction is aggravated, and the performance and the service life of the battery are seriously influenced. At present, the high-voltage electrolyte is generally designed by using a solvent with higher electronegativity to increase the oxidation potential of the electrolyte, such as fluoro-carbonate, fluoro-borate, sulfone solvents and fluoroether solvents. Recent reports also propose the use of ionic liquids and ultra-high concentration electrolytes to effectively solve the problem of oxidative decomposition of electrolytes under high pressure. However, the high cost of such electrolytes has hindered their ability to be practically used in the industry.
Disclosure of Invention
The invention aims to provide the electrolyte for the high-voltage lithium metal battery, which can work stably for a long time under the high voltage of more than 4.5V, has obvious cost advantage and is suitable for large-scale use. The invention is carried out according to the following embodiments.
An electrolyte usable for a high voltage lithium metal battery, which is in a liquid state, and is composed of a metal lithium salt, an organic solvent and an additive, wherein the metal lithium salt is composed of lithium hexafluorophosphate and a boron-containing lithium salt, and the concentration of the lithium hexafluorophosphate in the electrolyte is greater than that of the boron-containing lithium salt; the organic solvent consists of Hydrofluoroether (HFE), cyclic carbonate and linear carbonate; the additive is one or more of tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite or difluoro diphosphoric acid bis (trimethylsilyl); the additive accounts for 0.1-5% of the total mass of the electrolyte, the organic solvent accounts for 60-90% of the total mass of the electrolyte, and the balance is the metal lithium salt. The tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite or bis (trimethylsilyl) difluorodiphosphonate referred to in this application is collectively referred to as "methylsilyl (phosphite"
The boron-containing lithium salt used is selected from lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium bis (oxalato) borate (LiBOB) or lithium difluoro (oxalato) borate (lidob), preferably lithium difluoro (oxalato) borate (lidob).
The organic solvent contains one or two of cyclic carbonate selected from Ethylene Carbonate (EC) or Propylene Carbonate (PC), and linear carbonate selected from one or more of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) or diethyl carbonate (DEC), preferably.
In experiments, the ratio of the hydrofluoroether to the total mass of cyclic carbonate and linear carbonate in the organic solvent is found to be (0.2-2): 1, the mass ratio of the cyclic carbonate to the linear carbonate is (0.1-1): 1, the electrolyte has better performance and the material consumption is proper.
A lithium metal battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein the positive electrode is formed by coating positive electrode slurry formed by mixing an active substance which is a ternary positive electrode active material, a conductive agent carbon black and a binder polyvinylidene fluoride according to the weight ratio of 8:1:1 on a positive electrode current collector Al foil, the negative electrode is a metal lithium sheet, and the diaphragm is a diaphragm commonly used by the existing lithium ion battery, such as polyethylene, polypropylene, polytetrafluoroethylene, polyththalimide and the like; the electrolyte adopts the electrolyte which can be used for the high-voltage lithium ion battery, and the shell can be an aluminum shell, soft plastic and the like; wherein the ternary positive active material adopts a lithium-rich manganese-based or high-nickel ternary material, such as Li [ ] 0.2 Mn 0.53 Ni 0.27 ]O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 And the like. And assembling by adopting the conventional assembly process of the lithium ion battery. The charge cut-off voltage of the battery is 4.5-4.9V.
Compared with the prior electrolyte for the lithium metal battery, the invention has the following advantages:
1. the invention particularly selects the scheme that the adopted lithium salt is lithium hexafluorophosphate, boron-containing lithium salt and a specific methyl silicon-based (phosphite) phosphate additive, the boron-containing lithium salt and the additive have obvious synergistic effect, and the voltage window can be obviously improved. Compared with other high-solubility metal lithium salts such as LiFSI and LiTFSI, the lithium hexafluorophosphate has higher electrochemical stability and can be used in a high-voltage working environment of more than 4.5V. The boron-containing lithium salt reacts with oxygen free radicals in the electrolyte to form firm LI-B-O and B-O bonding components, so that a firmer interface is constructed to inhibit the decomposition of the electrolyte and the dissolution of transition metal, and the methyl silicon-based (phosphite) phosphate additive directionally captures HF, so that the damage of HF to the electrolyte interface is reduced, ammonium salt precipitation is not generated, side reaction is avoided, and the performance of the battery is further improved.
2. Compared with other electrolyte technical schemes under high voltage, for example, a solvent system with strong electronegativity such as a fluoro solvent and a sulfone solvent is used, although the oxidation potential of the electrolyte can be effectively increased, the fluoro solvent can inevitably generate harmful acidic substances such as HF, the oxidation decomposition potential of the sulfone solvent is over 5.5V, most of the sulfone solvents are solid at room temperature, the viscosity is high, the conductivity is low, and the cost is high and the wide application is difficult. The use of the high-concentration lithium salt can effectively increase the stability of an electrolyte system, greatly improve the production cost and have no economic benefit. The use of other novel lithium salts or additives, such as LiDFP, can effectively optimize the film-forming component and reduce the impedance, but the lithium salts or additives have low solubility per se, poor oxidation stability and are not applicable under a high-pressure system; the nitrile additive has good oxidation resistance, but is easy to polymerize in graphite or lithium metal negative electrodes to influence the de-intercalation of lithium ions; the common carbonate additive has low cost and good film forming effect, but is faced with more serious CO in the circulating process 2 The problem of gas generation. The scheme of the invention has the advantages of low consumption of the boron-containing lithium salt and the methyl silicon-based (phosphite) phosphate additive, obvious effect, cost advantage, no side effect, simple preparation and higher practical value.
3. The organic solvent of the invention also particularly selects a scheme of combining the hydrofluoroether with two different types of carbonic acid esters, not only fully utilizes the excellent oxidation stability of the hydrofluoroether solvent, but also has obvious cost advantage. The combination of the cyclic carbonate and the linear carbonate, the high dielectric constant of the cyclic ester and the low viscosity of the linear ester are utilized, so that the electrolyte has the advantages of high ionic conductivity and wide liquid range under the condition of ensuring that lithium salt is fully dissolved and dissociated, and is suitable for being used in different temperature ranges. The scheme has practical benefit and application prospect for realizing a lithium metal electrolyte system with low cost and high voltage stability.
Drawings
FIG. 1 LSV curves for example 1 and comparative example 1
Detailed Description
Example 1
A lithium metal battery was prepared by the following procedure.
(1) Preparing a positive plate: the lithium-rich manganese-based positive electrode active material Li [ Li ] 0.2 Mn 0.53 Ni 0.27 ]O 2 The conductive agent carbon black and the adhesive polyvinylidene fluoride (PVDF) are fully stirred and mixed in a proper amount of n-methyl pyrrolidone (NMP) solvent according to the weight ratio of 8:1:1 to form uniform anode slurry; and coating the positive electrode slurry on a positive electrode current collector Al foil, and drying and rolling to obtain the positive electrode piece.
(2) And (3) negative plate: a lithium sheet with a thickness of 0.6 to 1.5mm is used as a negative electrode.
(3) And (3) isolation film: a polypropylene (PP) porous polymer film is used as a separation film.
(4) Preparation of electrolyte that can be used for high voltage lithium metal batteries: in a dry argon atmosphere glove box, Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) are mixed according to the mass ratio of EC: DMC: EMC of 1:2:2, and after complete clarification, a hydrofluoroether solvent is added, wherein the mass of the hydrofluoroether solvent is 15% of the total solvent mass. Followed by addition of lithium salt LiPF 6 Dissolving and fully stirring, adding lithium salt LiDFOB containing boron, mixing and clarifying, adding an additive, and uniformly stirring to obtain the electrolyte. Wherein, LiPF 6 The concentration of (2) was 0.9mol/l and the concentration of LiDFOB was 0.1 mol/l. The additive is tris (trimethylsilyl) phosphate (TMSP) accounting for 2 wt% of the total mass of the electrolyte, and the organic solvent accounts for 86 wt% of the total mass of the electrolyte.
(5) Preparing a lithium ion battery: and assembling the button cell in a glove box with the water content less than 0.5ppm, wherein the battery case is 2016 type battery case. And (3) stacking the positive battery shell, the positive plate, the isolating membrane, the negative plate and the negative battery shell in sequence to enable the isolating membrane to be positioned between the positive plate and the negative plate to play an isolating role, and dripping 35ul of the electrolyte prepared in the step (4) on two sides of the isolating membrane respectively. And packaging to obtain the button cell.
Comparative example 1:basically the same preparation method as that of example 1 is adopted, but the electricity used by the lithium ion battery commonly used in the prior art is adoptedAnd (4) decomposing the solution to obtain the battery of comparative example 1. The LSV curve of the cells obtained under the same test conditions is shown in figure 1. As can be seen from fig. 1, the electrochemical window of the electrolyte is greatly improved in the battery of example 1 due to the addition of the hydrofluoroether solvent, the boron-containing lithium salt and the methylsilyl (phosphite) phosphate additive, and the oxidation potential is increased from 4.6V of comparative example 1 to 5.3V of example 1.
Example 2:essentially identical to the preparation process of example 1, except that: the additive used in the electrolyte is 2 wt.% TMSP of the total mass of the electrolyte, and 0.9mol/l LiPF 6 The amount of the boron-containing lithium salt was 0.2mol/l of LiDFOB.
Example 3:essentially identical to the preparation process of example 1, except that: the additive used in the electrolyte was 0.5 wt.% tris (trimethylsilyl) phosphite (TMSPi),1.1mol/l LiPF based on the total mass of the electrolyte 6 The amount of the boron-containing lithium salt was 0.1mol/l of LiDFOB.
Example 4:essentially identical to the preparation process of example 1, except that: the additive used in the electrolyte is 1 wt.% TMSPi,1mol/l LiPF of the total mass of the electrolyte 6 The amount of the boron-containing lithium salt was 0.05mol/l of LiDFOB.
Example 5:essentially identical to the preparation process of example 1, except that: the positive active material of the positive plate is high-nickel ternary active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 。
Example 6:essentially identical to the preparation process of example 1, except that: the active substance of the positive plate is high-nickel ternary active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 The additive used was 2 wt.% TMSPi and LiPF with a lithium salt concentration of 0.9mol/l 6 The amount of the boron-containing lithium salt was 0.2mol/l of LiDFOB.
Example 7:the cut-off voltage of the battery using the preparation method of example 1 during the test was 2.0V to 4.9V.
Comparative example 2:essentially identical to the preparation process of example 1, except that: electric powerNo additive and no hydrofluoroether solvent are used in the electrolyte.
Comparative example 3:essentially identical to the preparation process of example 1, except that: the additive used in the electrolyte was 1 wt.% TMSP of the total mass of the electrolyte, and no hydrofluoroether solvent was added.
Comparative example 4:essentially identical to the preparation process of example 1, except that: the active substance of the positive plate is high-nickel ternary active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiPF with 1mol/l lithium salt without additive 6 No hydrofluoroether solvent was added.
Comparative example 5:essentially identical to the preparation process of example 1, except that: the active substance of the positive plate is high-nickel ternary active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 The additive used was 1 wt.% TMSP of the total mass of the electrolyte, with no hydrofluoroether solvent added.
The lithium salt and additives in the electrolytes of the above examples and comparative examples are shown in table 1.
TABLE 1 cases of the medium lithium salt, additive, of comparative examples 1 to 5 and examples 1 to 7
The solvent parameters of the electrolytes in the above examples and comparative examples are shown in table 2.
TABLE 2 solvent compounding ratio parameters for comparative examples 1 to 5 and Experimental examples 1 to 7
The positive electrode active materials used in the examples and comparative examples are shown in table 3.
TABLE 3 conditions of positive electrode active materials used in comparative examples 1 to 5 and examples 1 to 7
| Positive electrode active material | |
| Comparative example 1 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Comparative example 2 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Comparative example 3 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Comparative example 4 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 |
| Comparative example 5 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 |
| Example 1 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Example 2 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Example 3 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Example 4 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
| Example 5 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 |
| Example 6 | LiNi 0.6 Co 0.2 Mn 0.2 O 2 |
| Example 7 | Li[Li 0.2 Mn 0.53 Ni 0.27 ]O 2 |
The button lithium metal batteries of examples 1 to 7 and comparative examples 1 to 5 described above were subjected to a 30 ℃ constant temperature cycle test using the following method:
(1) the positive electrode active material is a lithium-rich manganese-based active material (Li [ Li ]) 0.2 Mn 0.53 Ni 0.27 ]O 2 ) The 30 ℃ constant temperature cycle test method of the battery comprises the following steps: the lithium ion batteries except for example 7 were charged at 30 ℃ with a 0.1C constant current of 4.7V and then discharged at a 0.1C constant current to 2.0V; then charging the lithium ion battery to 4.65V at a constant current and a constant voltage of 1C, stopping the current to 0.035mA, discharging to 2.0V at a constant current of 1C, and recording the discharge capacity at the moment as d 1 And the discharge capacity at this time was recorded as d after 200 cycles 2 . Each group was tested for 15 lithium ion batteries and the average was taken.
Examples7, carrying out a separate high-pressure cycle test by the following test method: charging the lithium ion battery at a constant current of 0.1 ℃ for 4.9V, and then discharging at a constant current of 0.1C to 2.0V; then charging the lithium ion battery to 4.9V at a constant current of 1C, discharging to 2.0V at a constant current of 1C, and recording the discharge capacity at the moment as d 1 And the discharge capacity at this time was recorded as d after 200 cycles 2 。
(2) The positive active material is high-nickel ternary active material (LiNi) 0.6 Co 0.2 Mn 0.2 O 2 ) The 30 ℃ constant temperature cycle test method of the lithium metal battery comprises the following steps: charging the lithium ion battery at a constant current of 0.1 ℃ for 4.6V at 30 ℃, and then discharging at a constant current of 0.1C to 2.8V; and then charging the lithium ion battery to 4.6V at a constant current of 1C, discharging to 2.8V at a constant current of 1C, and recording the discharge capacity at the moment as d 1 And the discharge capacity at this time was recorded as d after 200 cycles 2 . Each group was tested for 15 lithium ion batteries and the average was taken.
Lithium metal battery capacity retention rate [ d ] at 30 DEG C 2 /d 1 ]×100％。
The button lithium metal batteries of examples 1 to 7 and comparative examples 1 to 5 described above were subjected to a voltage stability test using the following method.
(1) The positive electrode active material is a lithium-rich manganese-based active material (Li [ Li ]) 0.2 Mn 0.53 Ni 0.27 ]O 2 ) Cell voltage stability test of (2): the lithium ion batteries except for example 7 were charged at 30 ℃ to 4.7V at a constant current of 0.1C and then discharged at a constant current of 0.1C to 2.0V; then charging the lithium ion battery to 4.65V with a constant current and a constant voltage of 1C, discharging the lithium ion battery to 2.0V with a constant current of 1C and a cutoff current of 0.035mA, and recording the discharge median voltage at the moment as V 1 Cycling 200 times, recording the discharge median voltage at this time as V 2 . Each group was tested for 15 lithium ion batteries and the average was taken.
Example 7 a separate voltage stability test was performed by: charging the lithium ion battery to 4.9V at a constant current of 0.1C at 30 ℃, and then discharging to 2.0V at a constant current of 0.1C; then charging the lithium ion battery to 4.9V at a constant current and a constant voltage of 1C, discharging to 2.0V at a constant current of 1C, and recording the discharge median voltage at the moment as V 1 Cycle 200 times, record this timeDischarge median voltage of V 2 . Each group was tested for 15 lithium ion batteries and the average was taken.
(2) The positive active material is high-nickel ternary active material (LiNi) 0.6 Co 0.2 Mn 0.2 O 2 ) Cell voltage stability test of (2): charging the lithium ion battery to 4.6V at a constant current of 0.1C at 30 ℃, and then discharging to 2.8V at a constant current of 0.1C; then charging the lithium ion battery to 4.6V at a constant current of 1C, discharging to 2.8V at a constant current of 1C, and recording the discharge median voltage at the moment as V 1 Cycling 200 times, recording the discharge median voltage at this time as V 2 . Each group was tested for 15 lithium ion batteries and the average was taken.
The voltage stability of the lithium metal battery is compared according to the median voltage difference, wherein the median voltage difference is V 2 -V 1 。
The results of the 30 ℃ capacity retention and voltage stability tests are shown in Table 4.
Performance test results of capacity retention ratio and voltage stability at 430 ℃ in Table
As seen from the results of the performance tests of the above comparative examples and examples of table 4, the cycle performance and voltage stability of the battery were poor without adding the boron-containing lithium salt and the additive; after the lithium salt containing boron is added, the cycle performance and the voltage stability are obviously improved. Meanwhile, the boron-containing lithium salt and the methyl silicon-based (phosphite) phosphate compound additive are used, so that the voltage stability of the battery is further improved, and the battery has good cycle performance. And the addition of the hydrofluoroether solvent can better improve the high-pressure cycle performance of the electrolyte and show better long-term service life.
It should be further noted that the methylsilyl (phosphite) phosphate compounds represented by TMSP and TMSPi have the ability to directionally scavenge HF in the electrolyte and form films, so that they have a significant effect on the voltage stability of the positive electrode material. The methyl silicon-based (phosphite) phosphate reacts with trace HF components in the electrolyte to form a silicon element derived CEI film, so that the decomposition of lithium salt and a solvent is inhibited, the interface stability between the positive electrode and the electrolyte and the interface stability between the negative electrode and the electrolyte are effectively improved, and the capacity, the normal-temperature cycle life, the rate capability and the voltage stability of the lithium ion battery are improved.
The boron-containing lithium salt has a lower Highest Occupied Molecular Orbital (HOMO) energy level, shows excellent oxidation stability, and can participate in the formation of an electrode/electrolyte interface film, so that the stability of an electrode and an electrolyte interface is improved, and the performance of the battery is obviously improved. In the examples, the LiDFOB is a representative of the boron-containing lithium salt, and other boron-containing lithium salts can also play the same role as the LiDFOB, and are also applicable to the electrolyte of the invention, which is not listed.
Claims (5)
1. An electrolyte for a high voltage lithium metal battery, which is in a liquid state and comprises a metal lithium salt, an organic solvent and an additive, wherein the electrolyte comprises: the metal lithium salt consists of lithium hexafluorophosphate and boron-containing lithium salt, and the concentration of the lithium hexafluorophosphate in the electrolyte is greater than that of the boron-containing lithium salt; the organic solvent consists of hydrofluoroether, cyclic carbonate and linear carbonate; the additive is one or more of tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite or difluoro diphosphoric acid bis (trimethylsilyl); the additive accounts for 0.1-5% of the total mass of the electrolyte, the organic solvent accounts for 60-90% of the total mass of the electrolyte, and the balance is the metal lithium salt.
2. The electrolyte usable in a high-voltage lithium metal battery according to claim 1, wherein: the boron-containing lithium salt is selected from one or more of lithium tetrafluoroborate, lithium bis (oxalato) borate or lithium difluoro (oxalato) borate.
3. The electrolyte usable in a high-voltage lithium metal battery according to claim 1 or 2, wherein: the cyclic carbonate in the organic solvent is selected from one or two of ethylene carbonate or propylene carbonate, and the linear carbonate is selected from one or more of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate.
4. The electrolyte usable in a high-voltage lithium metal battery according to claim 3, wherein: the ratio of the hydrofluoroether to the total mass of cyclic carbonate and linear carbonate in the organic solvent is (0.2-2): 1, the mass ratio of the cyclic carbonate to the linear carbonate is (0.1-1): 1.
5. a lithium metal battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein the positive electrode is formed by coating positive electrode slurry formed by mixing active substances, namely a ternary positive electrode active material, a conductive agent, carbon black and a binder, namely polyvinylidene fluoride according to the weight ratio of 8:1:1, on a positive electrode current collector Al foil, and the negative electrode is a metal lithium sheet, and is characterized in that: the electrolyte adopts the electrolyte which can be used for the high-voltage lithium ion battery and is disclosed in any one of claims 1-4; the charge cut-off voltage of the battery is 4.5-4.9V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210517854.1A CN114824481A (en) | 2022-05-13 | 2022-05-13 | Electrolyte for high-voltage lithium metal battery and lithium metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210517854.1A CN114824481A (en) | 2022-05-13 | 2022-05-13 | Electrolyte for high-voltage lithium metal battery and lithium metal battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114824481A true CN114824481A (en) | 2022-07-29 |
Family
ID=82513972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210517854.1A Pending CN114824481A (en) | 2022-05-13 | 2022-05-13 | Electrolyte for high-voltage lithium metal battery and lithium metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114824481A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104934638A (en) * | 2015-04-24 | 2015-09-23 | 江苏华盛精化工有限责任公司 | High-voltage electrolyte for lithium ion battery |
| WO2018096889A1 (en) * | 2016-11-24 | 2018-05-31 | 日本電気株式会社 | Non-aqueous electrolyte solution and lithium ion secondary battery |
| CN110085913A (en) * | 2019-05-23 | 2019-08-02 | 河南电池研究院有限公司 | It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof |
| CN110931873A (en) * | 2019-12-11 | 2020-03-27 | 中国科学院山西煤炭化学研究所 | Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system |
| CN111244553A (en) * | 2020-03-23 | 2020-06-05 | 成都新柯力化工科技有限公司 | Safety electrolyte for lithium nickel phosphate high-voltage lithium battery |
| CN111326799A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof |
| CN112909334A (en) * | 2019-11-19 | 2021-06-04 | 宁德国泰华荣新材料有限公司 | Electrolyte and lithium ion battery |
| CN113078357A (en) * | 2021-03-17 | 2021-07-06 | 东莞市杉杉电池材料有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery |
-
2022
- 2022-05-13 CN CN202210517854.1A patent/CN114824481A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104934638A (en) * | 2015-04-24 | 2015-09-23 | 江苏华盛精化工有限责任公司 | High-voltage electrolyte for lithium ion battery |
| WO2018096889A1 (en) * | 2016-11-24 | 2018-05-31 | 日本電気株式会社 | Non-aqueous electrolyte solution and lithium ion secondary battery |
| CN110085913A (en) * | 2019-05-23 | 2019-08-02 | 河南电池研究院有限公司 | It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof |
| CN112909334A (en) * | 2019-11-19 | 2021-06-04 | 宁德国泰华荣新材料有限公司 | Electrolyte and lithium ion battery |
| CN110931873A (en) * | 2019-12-11 | 2020-03-27 | 中国科学院山西煤炭化学研究所 | Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system |
| CN111326799A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof |
| CN111244553A (en) * | 2020-03-23 | 2020-06-05 | 成都新柯力化工科技有限公司 | Safety electrolyte for lithium nickel phosphate high-voltage lithium battery |
| CN113078357A (en) * | 2021-03-17 | 2021-07-06 | 东莞市杉杉电池材料有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| GANESAN NAGASUBRAMANIAN，ET AL.: "Hydrofluoroether electrolytes for lithium-ion batteries: Reduced gas decomposition and nonflammable", 《JOURNAL OF POWER SOURCES》, vol. 196, 6 June 2011 (2011-06-06), pages 8604 - 8609, XP055917060, DOI: 10.1016/j.jpowsour.2011.05.078 * |
| 詹元杰等人: ""基于碳酸酯基电解液的4.5 V电池"", 《储能科学与技术》, vol. 9, no. 2, 5 March 2020 (2020-03-05), pages 319 - 330 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336078B (en) | Silicon-based negative electrode electrolyte and lithium ion power battery | |
| CN111883839B (en) | High-voltage electrolyte and lithium ion battery based on same | |
| CN111653829A (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN114122491A (en) | Lithium ion battery | |
| CN105406124B (en) | A kind of electrolyte improving high-temperature lithium ion battery and high voltage capability and its application in lithium ion battery | |
| CN111384443B (en) | Battery electrolyte additive, electrolyte using same and lithium ion battery | |
| CN108232296B (en) | Electrolyte solution and lithium secondary battery | |
| CN105914402B (en) | A kind of nonaqueous electrolytic solution and lithium ion battery | |
| CN112635835B (en) | High-low temperature compatible non-aqueous electrolyte and lithium ion battery | |
| CN109935908B (en) | Low-concentration lithium salt electrolyte and lithium secondary battery comprising same | |
| CN110875490B (en) | Lithium ion battery and preparation method thereof | |
| KR20120089197A (en) | Electrolyte for electrochemical device and the electrochemical device thereof | |
| CN113078354A (en) | Ternary lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN103346350A (en) | Electrolyte for improving performance of lithium ion battery and battery | |
| CN112310473A (en) | High-low temperature lithium ion battery electrolyte and lithium ion battery | |
| CN112467203A (en) | High-voltage-resistant non-aqueous electrolyte for lithium ion battery and ternary high-voltage lithium ion battery | |
| CN113809401A (en) | Non-aqueous electrolyte of lithium ion battery and application thereof | |
| CN113991178A (en) | Non-aqueous electrolyte of lithium ion battery and application thereof | |
| CN112713307A (en) | High-voltage non-aqueous electrolyte and lithium ion battery based on same | |
| CN108832180B (en) | Lithium ion battery electrolyte and lithium ion battery containing same | |
| CN111129589A (en) | Ternary high-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN114188606B (en) | Electrolyte and application thereof | |
| CN116031485A (en) | High-density high-safety lithium ion battery electrolyte and lithium ion battery | |
| CN113964385B (en) | Electrolyte, preparation method and application thereof | |
| CN106941191B (en) | Lithium ion battery and non-aqueous electrolyte thereof |
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 |