CN107134592A - A kind of fluoro ether electrolyte for lithium cells and preparation method thereof - Google Patents
A kind of fluoro ether electrolyte for lithium cells and preparation method thereof Download PDFInfo
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- CN107134592A CN107134592A CN201710500538.2A CN201710500538A CN107134592A CN 107134592 A CN107134592 A CN 107134592A CN 201710500538 A CN201710500538 A CN 201710500538A CN 107134592 A CN107134592 A CN 107134592A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of fluoro ether electrolyte for lithium cells and preparation method thereof.Compared with the existing electrolyte for lithium cells based on ethers, the present invention prepare to electrolyte show the compatibility good with high-voltage positive electrode material and graphite cathode material, while also significantly improving the cyclicity and fire resistance of high pressure material/lithium half-cell and graphite/lithium half-cell.In a word, it is of the invention by 1,1,2, the trifluoroethyl ether (HFE 347) of 2 four fluoro ethyl 2,2,2 is introduced into lithium battery electrolytes, so as to obtain a kind of novel electrolyte system combinations, preparation method of the present invention is simple, it is easy to carry out large-scale industrial production, the value of great business promotion.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of fluoro ether electrolyte for lithium cells and its preparation side
Method.
Background technology
Security is the subject matter of large-scale lithium battery development, the right and wrong in many applications such as electric tool and electric vehicle
Often need.Although many factors may cause the unsafe acts of lithium battery, the one of the main reasons of potential safety hazard is
Electrolyte solvent discharges excessive heat and causes the thermal runaway of battery to the oxidation reaction of powered positive electrode.Often at present
The organic solvent seen be alkylcarbonic acid esters compound and material of organic ethers compound, but carbonats compound flash-point all very
It is low, cause the electrolyte solution (electrolyte) of lithium ion battery easily to burn, and ether organic solvent is negative to business graphite
It is extremely incompatible.Therefore probe into that oxidative resistance is high and the electrolyte compatible to commercial graphite negative pole be current lithium battery direction weight
Want one of problem.
Fluorinated organic solvent is applied in lithium ion battery always for a long time, the conventional electrolysis matter phase with non-fluorinated solvents
Than fluorated solvent can be the various benefits of electrolyte carry.For example, fluorination cyclic carbonate is used by McMillan and Nanbu
Make electrolyte solvent.Smart et al. designs have synthesized a series of fluorinated linear carbonic esters, and the serial fluoro carbonic ester is navigated in the U.S.
The jet propulsion laboratory of empty space agency improves lithium ion battery in deep space application as new electrolyte components
Cryogenic property.Achiha, Koh and Arai et al. report respectively fluorocarbons acid esters and fluorinated ether can as non-flammable electrolyte or
The solvent of non-aqueous lithium ion cell electrolyte.Therefore, continuation is needed badly fluorinated organic solvent is furtherd investigate to expand it
Application in lithium cell electrolyte solution field.
The content of the invention
For above-mentioned the deficiencies in the prior art, there is provided a kind of resistance to oxidation with practical exploration by long-term technology by inventor
Performance height, good flame resistance and the electrolyte for lithium cells good to graphite cathode compatibility.
Specifically, the present invention relates to following technical scheme：
The first aspect of the invention exists there is provided 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347)
Prepare the application in fluoro ether electrolyte for lithium cells and/or fluoro ether lithium battery.Inventors be surprised to learn that, by lithium
1,1,2,2- tetra- fluoro ethyl -2,2 is added in battery electrolyte, 2- trifluoroethyls ether (HFE-347) can significantly improve whole lithium
Oxidation resistent susceptibility, fire resistance and the compatibility good to graphite cathode of battery system.Inventor, which studies, to be thought, 1,1,2,
The fluoro ethyls -2,2 of 2- tetra-, 2- trifluoroethyls ether (HFE-347) contributes to electrode interface to form excellent solid electrolyte interface film,
Improve the compatibility between electrolyte and active material, while intermolecular viscous force can be weakened so that molecule, the migration of ion
Resistance reduces, and then reduces viscosity, improves electrolytic conductivity, so that the cyclical stability and battery capacity that improve battery are protected
Holdup；Meanwhile, 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347) nature has well thermally-stabilised
Property, no flash-point, so as to significantly improve the flash-point of lithium battery electrolytes, efficiently solves the inflammable problem of electrolyte.
The second aspect of the invention includes there is provided a kind of fluoro ether electrolyte for lithium cells, the electrolyte：Fluoro
Ether；The fluoro-ether is the fluoro ethyl -2,2,2- trifluoroethyls ethers (HFE-347) of 1,1,2,2- tetra-；
It is preferred that, the fluoro-ether accounts for the 0.1%~99.9% of electrolyte solvent volume；
It is preferred that, the electrolyte also includes lithium salts and ethers cosolvent；
It is preferred that, the lithium salt is 0.01M~3M；
It is preferred that, the lithium salts is double trifluoromethanesulfonimide lithium (LiTFSI), LiPF6、LiClO4、LiAsF6、
LiBF4、LiCH3SO3、LiCF3SO3、LiBO、LiN(CF3SO2)2In one or more；
It is preferred that, the ethers cosolvent is tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, dimethoxy
One or more in methane, 1,2- dimethoxies, diethylene glycol dimethyl ether；
It is preferred that, the fluoro ether electrolyte for lithium cells is made up of ethers cosolvent, HFE-347 and lithium salts；
Wherein, the volume ratio of the ethers cosolvent and HFE-347 is 1:1~2, the lithium salt is 1M；
It is further preferred that the ethers cosolvent be tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes,
Any of dimethoxymethane, 1,2- dimethoxies, diethylene glycol dimethyl ether；
The lithium salts is LiTFSI, LiPF6、LiClO4、LiAsF6、LiBF4、LiCH3SO3、LiCF3SO3、LiBO、LiN
(CF3SO2)2Any of；
The third aspect of the present invention is including following there is provided a kind of preparation method of fluoro ether electrolyte for lithium cells
Step：
First mixed solution will be mixed to get after fluoro-ether and the water removal of ethers cosolvent, then will under conditions of anhydrous and oxygen-free
Lithium salts, which is added to mixed solution, can obtain fluoro ether electrolyte for lithium cells.
It is preferred that, lithium salts is added dropwise when adding mixed solution, prevents mixed solution from overheating bumping；
The fourth aspect of the present invention, disclose the lithium primary battery prepared by above-mentioned electrolyte, lithium secondary battery and
Lithium ion battery；
It is preferred that, the high-voltage positive electrode material of the lithium primary battery, lithium secondary battery and lithium ion battery is commercialization three
First pole piece, the negative pole is commercialization graphite cathode.
Beneficial effects of the present invention：Compared with the existing electrolyte for lithium cells based on ethers, prepared by the present invention arrives
Electrolyte shows the compatibility good with high-voltage positive electrode material and graphite cathode material, while also significantly improving high pressure
The cyclicity and fire resistance of material/lithium half-cell and graphite/lithium half-cell.Data display is factually tested, in the electricity of ternary/lithium half
After pond is circulated 40 weeks, its capability retention is 97.41%；Graphite/lithium half-cell can form stable interface, and specific capacity
Still there are 271.7878mAh g after circulating 30 weeks-1.Determined, substituted with fluoro-ether HFE-347 existing by self-extinguishing time method
After common ethers, self-extinguishing time shortens 20.41%.Therefore, HFE bases electrolyte has higher security performance and anti-flammability,
And the chemical property of high-voltage positive electrode material and graphite cathode material can be improved.
To sum up, the present invention is by 1,1,2,2- tetra- fluoro ethyl -2,2, and 2- trifluoroethyls ether (HFE-347) introduces lithium battery electrolysis
In liquid, so that a kind of novel electrolyte system combinations are obtained, experiment proves that, the electrolyte system oxidation resistent susceptibility is high, resistance
Combustion property is well simultaneously good to graphite cathode compatibility, and preparation method of the present invention is simple, it is easy to carry out large-scale industrial production, great
The value of business promotion.
Brief description of the drawings
Fig. 1 is cyclic voltammetry curve of the battery of the offer of embodiment 1 under 0.5mV sweep speeds；
Fig. 2 is embodiment 1 and the battery of the offer of comparative example 1 in 500mA g-1Size of current discharge capacity and cycle-index
Graph of a relation；
Fig. 3 is cyclic voltammetry curve of the battery of the offer of embodiment 2 under 0.5mV sweep speeds；
Fig. 4 is embodiment 2 and the battery of the offer of comparative example 2 in 50mA g-1Size of current discharge capacity and cycle-index
Graph of a relation.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As background technology is introduced, need continuation badly and fluorinated organic solvent is furtherd investigate to expand it in lithium electricity
Application in the electrolyte solution field of pond；
In view of this, there is provided 1,1,2,2- tetra- fluoro ethyl -2,2,2- trifluoros in a kind of embodiment of the invention
Application of the ethylether (HFE-347) in fluoro ether electrolyte for lithium cells and/or fluoro ether lithium battery is prepared.1,1,2,
2- tetra- fluoro ethyl -2,2,2- trifluoroethyls ether (HFE-347) its structural formula is as follows：
It individually or can mix other solvents and use as a kind of environment-friendly type solvent, usually as cleaning agent, drier,
Or the auxiliary agent of removing dust or on-condensible gas is used, inventor has been surprisingly found that under study for action, by into lithium battery electrolytes
1,1,2,2- tetra- fluoro ethyls -2,2 are added, 2- trifluoroethyls ether (HFE-347) can significantly improve the resistance to of whole lithium battery system
Oxidation susceptibility, fire resistance and the compatibility good to graphite cathode.
There is provided a kind of fluoro ether electrolyte for lithium cells, the electrolyte in the still another embodiment of the present invention
Including：Fluoro-ether；The fluoro-ether is the fluoro ethyl -2,2,2- trifluoroethyls ethers (HFE-347) of 1,1,2,2- tetra-；
Wherein, the fluoro-ether accounts for the 0.1%~99.9% of electrolyte solvent volume；
The electrolyte also includes lithium salts and ethers cosolvent；
The lithium salt is 0.01M~3M；
The lithium salts is double trifluoromethanesulfonimide lithium (LiTFSI), LiPF6、LiClO4、LiAsF6、LiBF4、
LiCH3SO3、LiCF3SO3、LiBO、LiN(CF3SO2)2In one or more；
The ethers cosolvent be tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, dimethoxymethane, 1,
One or more in 2- dimethoxies, diethylene glycol dimethyl ether；
The present invention still another embodiment in, the fluoro ether electrolyte for lithium cells by ethers cosolvent,
HFE-347 and lithium salts composition；
Wherein, the volume ratio of the ethers cosolvent and HFE-347 is 1:1~2, the lithium salt is 1M；
The ethers cosolvent be tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, dimethoxymethane, 1,
Any of 2- dimethoxies, diethylene glycol dimethyl ether；
The lithium salts is LiTFSI, LiPF6、LiClO4、LiAsF6、LiBF4、LiCH3SO3、LiCF3SO3、LiBO、LiN
(CF3SO2)2Any of；
There is provided a kind of preparation side of fluoro ether electrolyte for lithium cells in the still another embodiment of the present invention
Method, comprises the following steps：
First mixed solution will be mixed to get after fluoro-ether and the water removal of ethers cosolvent, then will under conditions of anhydrous and oxygen-free
Lithium salts, which is added to mixed solution, can obtain fluoro ether electrolyte for lithium cells.
Lithium salts is added dropwise when adding mixed solution, prevents mixed solution from overheating bumping；
In the still another embodiment of the present invention, the lithium primary battery prepared by above-mentioned electrolyte, lithium are disclosed
Secondary cell and lithium ion battery；
Wherein, the high-voltage positive electrode material of the lithium primary battery, lithium secondary battery and lithium ion battery is commercialization ternary
Pole piece, the negative pole is commercialization graphite cathode.
Below by instantiation, the present invention will be further elaborated, it should explanation, the description below be only for
The present invention is explained, its content is not defined.
Embodiment 1：Described organic solvent composition and each composition percent by volume are：1,3- dioxolanes/HFE-347
(volume ratio)=1/1, double trifluoromethanesulfonimide lithium concentrations are 1.0M.
Ternary pole piece, metal pole piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery, then
Sealing, is assembled into button cell.
Embodiment 2：Described organic solvent composition and each composition percent by volume are：1,3- dioxolanes/HFE-347
(volume ratio)=1/1, double trifluoromethanesulfonimide lithium concentrations are 1.0M.
Graphite pole piece, metal pole piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery, then
Sealing, is assembled into button cell.
Embodiment 3：Described organic solvent composition and each composition percent by volume are：Tetrahydrofuran/HFE-347 (volumes
Than)=1/1, hexafluoroarsenate lithium concentration is 1.0M.
Ternary pole piece, metal pole piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery, then
Sealing, is assembled into button cell.
Embodiment 4：Described organic solvent composition and each composition percent by volume are：2- methyltetrahydrofurans/HFE-347
(volume ratio)=1/1, tetrafluoro boric acid lithium concentration is 1.0M.
Tertiary cathode piece, lithium anode piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery,
Then seal, be assembled into button cell.
Embodiment 5：Described organic solvent composition and each composition percent by volume are：Diethylene glycol dimethyl ether/HFE-347
(volume ratio)=1/1, hexafluoroarsenate lithium concentration is 1.0M.
Tertiary cathode piece, lithium anode piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery,
Then seal, be assembled into button cell.
Embodiment 6：Described organic solvent composition and each composition percent by volume are：1,3- dioxolanes/HFE-347
(volume ratio)=1/2, hexafluorophosphoric acid lithium concentration is 1.0M.
Tertiary cathode piece, lithium anode piece, barrier film, electrolyte and battery plus-negative plate shell stacked group are dressed up into battery,
Then seal, be assembled into button cell.
Comparative example 1：With embodiment 1 except that, fluoro-ether has been substituted for glycol dimethyl ether in electrolyte
(DME), other parts be the same as Example 1, is assembled into battery.
Comparative example 2：With embodiment 2 except that, fluoro-ether has been substituted for glycol dimethyl ether in electrolyte
(DME), other parts be the same as Example 2, is assembled into battery.
Cyclic voltammetric and electrochemical property test
Cyclic voltammetry is carried out to embodiment 1, sweep speed is 0.5mV/s, and voltage range is 3.0V to 4.3V.
Cyclic voltammetry is carried out to embodiment 2, sweep speed is 0.5mV/s, and voltage range is 0.005V to 3.000V.
Chemical property detection is carried out to embodiment 1-5 and comparative example 1-2 battery respectively, at room temperature respectively in voltage
Scope is to be tested in 3.0V to 4.3V.
Chemical property detection is carried out to the battery of embodiment 2, arrived respectively in voltage range for 0.005V at room temperature
3.000V interior tested.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- Fluoro ethyl -2,2,2- trifluoroethyls the ethers of 1.1,1,2,2- tetra- are preparing fluoro ether electrolyte for lithium cells and/or fluoro Application in ether lithium battery.
- 2. a kind of fluoro ether electrolyte for lithium cells, it is characterised in that the electrolyte includes：Fluoro-ether；The fluoro-ether For the fluoro ethyl -2,2,2- trifluoroethyl ethers of 1,1,2,2- tetra-.
- 3. a kind of electrolyte as claimed in claim 2, it is characterised in that the fluoro-ether accounts for electrolyte solvent volume 0.1%~99.9%.
- 4. a kind of electrolyte as claimed in claim 2, it is characterised in that the electrolyte also includes lithium salts and ethers is molten altogether Agent；Wherein, the lithium salt is 0.01M~3M；The lithium salts is LiTFSI, LiPF6、LiClO4、LiAsF6、LiBF4、LiCH3SO3、LiCF3SO3、LiBO、LiN (CF3SO2)2In one or more；The ethers cosolvent is tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, dimethoxymethane, 1,2- bis- One or more in methoxyethane, diethylene glycol dimethyl ether.
- 5. a kind of electrolyte as claimed in claim 2, it is characterised in that the fluoro ether electrolyte for lithium cells is by ethers Cosolvent, HFE-347 and lithium salts composition；Wherein, the volume ratio of the ethers cosolvent and HFE-347 is 1:1~2, the lithium salt is 1M.
- 6. a kind of electrolyte as claimed in claim 5, it is characterised in that the ethers cosolvent is tetrahydrofuran, 2- methyl Any of tetrahydrofuran, 1,3- dioxolanes, dimethoxymethane, 1,2- dimethoxies, diethylene glycol dimethyl ether；The lithium salts is LiTFSI, LiPF6、LiClO4、LiAsF6、LiBF4、LiCH3SO3、LiCF3SO3、LiBO、LiN (CF3SO2)2Any of.
- 7. a kind of preparation method of fluoro ether electrolyte for lithium cells, it is characterised in that comprise the following steps：First mixed solution will be mixed to get after fluoro-ether and the water removal of ethers cosolvent, then by lithium salts under conditions of anhydrous and oxygen-free Fluoro ether electrolyte for lithium cells can be obtained to mixed solution by adding.
- 8. preparation method as claimed in claim 7, it is characterised in that lithium salts is added dropwise when adding mixed solution.
- 9. lithium primary battery, lithium secondary battery and lithium ion battery that any one of the claim 1-6 electrolyte is prepared.
- 10. lithium primary battery as claimed in claim 9, lithium secondary battery and lithium ion battery, it is characterised in that its high positive pressure Pole material is commercialization ternary pole piece, and the negative pole is commercialization graphite cathode.
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| CN109449487A (en) * | 2018-10-31 | 2019-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion battery high concentration electrolyte and preparation method thereof and lithium ion battery |
| CN109713367A (en) * | 2018-12-28 | 2019-05-03 | 安普瑞斯（南京）有限公司 | A kind of siliceous lithium ion battery with high energy density |
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| CN110010970A (en) * | 2019-04-24 | 2019-07-12 | 杉杉新材料（衢州）有限公司 | A kind of high-pressure solid ferric phosphate lithium ion battery nonaqueous electrolytic solution and lithium ion battery |
| CN110783586A (en) * | 2019-11-21 | 2020-02-11 | 华南师范大学 | High-power-density primary battery electrolyte and preparation method and application thereof |
| CN110797544A (en) * | 2019-09-30 | 2020-02-14 | 西安交通大学 | High-performance lithium primary battery and preparation method thereof |
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| CN111697264A (en) * | 2019-03-14 | 2020-09-22 | 深圳格林德能源集团有限公司 | High-voltage lithium ion battery electrolyte |
| CN113394443A (en) * | 2020-03-12 | 2021-09-14 | 通用汽车环球科技运作有限责任公司 | Concentrated electrolyte for capacitor-assisted batteries |
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