CN112713307A - High-voltage non-aqueous electrolyte and lithium ion battery based on same - Google Patents
High-voltage non-aqueous electrolyte and lithium ion battery based on same Download PDFInfo
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- CN112713307A CN112713307A CN202011606589.1A CN202011606589A CN112713307A CN 112713307 A CN112713307 A CN 112713307A CN 202011606589 A CN202011606589 A CN 202011606589A CN 112713307 A CN112713307 A CN 112713307A
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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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M2300/0017—Non-aqueous electrolytes
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Abstract
The invention relates to a high-voltage non-aqueous electrolyte and a lithium ion battery based on the same, wherein the high-voltage non-aqueous electrolyte comprises electrolyte lithium salt, a non-aqueous organic solvent and an additive, wherein the additive comprises 1, 3-propylene sultone and lithium difluorobis (oxalato) phosphate; wherein, the maximum empty molecular orbital level of the solvated lithium difluorobis (oxalato) phosphate is-7.45 eV and the minimum empty molecular orbital level is-0.18 eV according to the calculation of a B3LYP method in a density functional theory. In the initial charging cycle process, the electrolyte of the invention can more easily form a stable SEI film, the decomposition of the electrolyte and the increase of the direct current internal resistance of the battery are weakened, and the low-impedance growth and long-cycle performance of the battery at different temperatures can be ensured.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage non-aqueous electrolyte and a lithium ion battery based on the same.
Background
The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life and the like, so that the lithium ion battery is generally applied to the field of 3C consumer electronics products such as mobile phones and notebook computers, and in addition, along with the rapid development of new energy automobiles, the application of the lithium ion battery in the fields of power and energy storage is more and more common. With the increase of the endurance mileage of the electric vehicle and the gradual decrease of national subsidies, the requirement on the energy density of the power battery is higher and higher, and at present, the effective methods are to improve the voltage and the compaction density of the electrode active material and select a proper electrolyte.
In order to improve the capacity of the battery, a high-voltage positive electrode material is an effective way for improving the capacity density of the lithium ion battery, and under high voltage, electrolyte is easy to decompose, so that gas generation is serious, and the performance of a battery core is seriously influenced. In order to improve the high-temperature performance of the lithium battery, a sulfonic acid compound is introduced into an electrolyte system, for example, 1, 3-propylene sultone can effectively inhibit gas generation of the battery, but the additive is easy to cause increase of direct-current internal resistance of the battery.
Therefore, it is particularly important to develop more and more novel electrolytes matched with high-voltage cathode materials.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a high-voltage nonaqueous electrolyte, wherein lithium difluorobis (oxalato) phosphate is matched with 1, 3-propylene sultone for use, and the electrolyte disclosed by the invention can more easily form a stable SEI film in the initial charging cycle process, so that the decomposition of the electrolyte and the increase of the direct-current internal resistance of the battery are weakened, and the low-impedance growth and long-cycle performance of the battery at different temperatures can be ensured.
The first object of the present invention is to provide a high-voltage nonaqueous electrolytic solution comprising an electrolyte lithium salt, a nonaqueous organic solvent and an additive, the additive comprising 1, 3-propylene sultone and lithium difluorobis (oxalato) phosphate;
wherein, according to the calculation of a B3LYP method in the Density Functional Theory (DFT), the highest unoccupied molecular orbital (HOMO) energy level of the solvated lithium difluorobis (oxalato) phosphate is-7.45 eV, and the Lowest Unoccupied Molecular Orbital (LUMO) energy level is-0.18 eV.
Further, the additive also comprises one or more of 1, 3-propane sultone PS, fluoroethylene carbonate FEC, ethylene sulfate DTD and vinylene carbonate VC.
Further, the content of the electrolyte lithium salt is 10-20% of the total mass of the electrolyte.
Further, the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium difluorophosphate (LiPO)2F2) Lithium bis (fluorosulfonylimide) (LiFSI), lithium bis (trifluoromethanesulfonylimide) (LiTFSI), and lithium tetrafluoroborate (LiBF)4) One or more of them.
Further, the non-aqueous organic solvent is selected from one or more of a linear carbonate solvent, a cyclic carbonate solvent, a carboxylic acid ester solvent, and a fluorinated carbonate solvent.
Further, the straight-chain carbonate solvent is selected from one or more of ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate; the cyclic carbonate solvent is selected from one or more of ethylene carbonate and propylene carbonate; the carboxylic ester solvent is selected from one or more of ethyl acetate, ethyl propionate, methyl propionate, propyl butyrate and propyl acetate; the fluorinated carbonate solvent is selected from one or more of fluorinated ethylene carbonate, 1, 2-difluoroethylene carbonate, methyl trifluoroethyl carbonate and bis trifluoroethyl carbonate.
A second object of the present invention is to provide a lithium ion battery comprising: a positive electrode, a negative electrode, a separator between the positive electrode and the negative electrode, and the electrolyte;
the positive electrode includes a positive electrode active material;
the negative electrode comprises a negative current collector and a negative diaphragm arranged on the negative current collector, and the negative diaphragm comprises a negative active material, a negative conductive agent and a binder.
Further, the positive active material is selected from one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel manganese oxide, lithium cobalt manganese manganate, lithium-rich manganese-based material and ternary positive material, and the structural formula of the ternary positive material is LiNi1-x-y-zCoxMnyAlzO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1.
Further, the negative active material is selected from one or more of artificial graphite, natural graphite, silicon-oxygen compound, silicon-based alloy and active carbon; the negative electrode conductive agent is selected from one or more of acetylene black, conductive carbon black, carbon fiber, carbon nanotube and Ketjen black.
Further, the kind of the diaphragm is not particularly limited and may be selected according to actual requirements. Preferably, the diaphragm comprises a base film and a nano alumina coating coated on the base film, wherein the base film is at least one of PP, PE and PET, and the thickness of the nano alumina coating is 1.0-6.0 μm.
In the invention, the high-voltage non-aqueous electrolyte refers to a non-aqueous electrolyte suitable for a lithium ion battery under a high-voltage condition, and the high voltage specifically refers to a charging voltage of 4.1-5.5V.
The matching principle and the action of all substances in the lithium ion battery electrolyte are as follows:
in the process of charging and discharging of the lithium ion battery, main components and additives in the electrolyte can be decomposed and polymerized on the surfaces of a positive electrode and a negative electrode, and a polymer with large molecular weight can be separated out on the surface of the electrode and wraps the generated inorganic lithium salt to form a solid electrolyte membrane which can isolate the electrolyte and can conduct ions. The electrolyte formed by the electrolyte solvent is thick and loose, and is difficult to protect and isolate the electrolyte, so that the electrolyte can be thickened continuously, the battery impedance is increased, and continuous electrolyte loss is brought. In the present invention, PST is an excellent high-temperature film-forming additive, but the increase of the content thereof causes a problem of high film-forming resistance. The HOMO-LUMO energy level is an expansion of the electrochemical window and is an expression of the excited ability of the solvated molecules. Lithium difluorobis (oxalato) phosphate is a lithium salt additive, and is obtained by theoretical calculation, compared with a solvated lithium difluorobis (oxalato) phosphate molecule with a highest vacancy molecular orbital (HOMO) level of-7.45 eV and a lowest vacancy molecular orbital (LUMO) level of-0.18 eV, the oxidation-reduction film-forming interval of the lithium difluorobis (oxalato) phosphate molecule is enlarged, which means that a film-forming sequence with a highest vacancy molecular orbital (HOMO) level of-7.45 eV and a lowest vacancy molecular orbital (LUMO) level of-0.18 eV in a battery system moves backwards, can be linked with a high-pressure film-forming PST to form a film together, and due to excessive coordination number of central atoms of lithium difluorobis (oxalato) phosphate, the lithium difluorobis (oxalato) phosphate is easy to be re-bonded with an electrolyte film with similar groups around, so that the electrolyte film is prevented from continuously growing, a stable P end group is formed, the thickness and the stability of an electrode surface film are controlled, and the, Performance with long cycles.
By the scheme, the invention at least has the following advantages:
in the initial charging cycle process, the electrolyte of the invention can more easily form a stable SEI film, the decomposition of the electrolyte and the increase of the direct current internal resistance of the battery are weakened, and the low-impedance growth and long-cycle performance of the battery at different temperatures can be ensured.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
In the present invention, the electrolyte solution includes an electrolyte lithium salt selected from lithium hexafluorophosphate (LiPF), a non-aqueous organic solvent and an additive6) Lithium difluorophosphate (LiPO)2F2) Lithium bis (fluorosulfonylimide) (LiFSI), lithium bis (trifluoromethanesulfonylimide) (LiTFSI), and lithium tetrafluoroborate (LiBF)4) The non-aqueous organic solvent is selected from one or more of a linear carbonate solvent, a cyclic carbonate solvent, a carboxylic ester solvent and a fluorinated carbonate solvent, and the additive comprises 1, 3-propane sultone PS, 1, 3-propene sultone PST and lithium difluorobis (oxalate) phosphate LiODFP; wherein, according to the calculation of a B3LYP method in a Density Functional Theory (DFT), the highest unoccupied molecular orbital (HOMO) energy level of the solvated lithium difluorobis (oxalato) phosphate is-7.45 eV, and the Lowest Unoccupied Molecular Orbital (LUMO) energy level is-0.18 eV; also comprises one or more of fluoroethylene carbonate FEC, ethylene sulfate DTD and vinylene carbonate VC.
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The lithium ion secondary battery of the present invention is prepared by:
LiNi as positive electrode active material0.5Co0.2Mn0.3O2(LNCM), conductive agent acetylene black and adhesive polyvinylidene fluoride (PVDF) are fully stirred and mixed uniformly in an N-methyl pyrrolidone solvent system according to the mass ratio of 95: 3: 2, then the mixture is coated on an aluminum foil to be dried and cold-pressed, and a positive pole piece is obtained, wherein the compaction density of the positive pole piece is 3.45g/cm3。
Fully stirring and uniformly mixing a negative active material graphite, a conductive agent acetylene black, a binder Styrene Butadiene Rubber (SBR) and a thickening agent sodium carboxymethyl cellulose (CMC) in a deionized water solvent system according to a mass ratio of 96: 2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain a negative pole piece, wherein the compaction density of the negative pole piece is 1.65g/cm3。
Polyethylene (PE) with the thickness of 9 mu m is taken as a base film, and a nano aluminum oxide coating layer with the thickness of 3 mu m is coated on the base film to obtain the diaphragm.
And stacking the positive and negative pole pieces and the diaphragm made of polyethylene in a negative pole, diaphragm, positive pole and diaphragm mode, and ending with the negative pole to obtain the bare cell.
And (3) carrying out hot pressing on the naked electric core to ensure that polyvinylidene fluoride (PVDF) on the surface of the diaphragm bonds the pole pieces together. And (3) welding the lugs of the hot-pressed bare cell, placing the bare cell in an aluminum plastic film with a punched pit, and carrying out hot-melt packaging to obtain the pre-packaged battery with a liquid injection port. And (3) placing the pre-packaged battery in a vacuum furnace for fully baking and drying, injecting corresponding electrolyte from the liquid injection port, and packaging the liquid injection port in a vacuum environment to obtain the secondary battery.
The secondary battery of the present invention can be tested by the following method:
(1) initial discharge capacity and cycle test of secondary battery
The prepared battery is aged and placed on a clamp, the activated battery is charged to 4.3V at 25 ℃ by using a current of 1C, the voltage is constant to 0.05C, the battery is discharged to 2.8V by using 1C, and the discharge capacity is recorded. And recording initial DCR of the battery after the first circle of discharge, then performing a cycle test until the discharge capacity of the battery is 80% of the first circle of capacity, and recording the DCR, the increase rate of the DCR, the number of turns of the battery reaching 80% SOH (state of health of the battery) and the change of gas production volume of the battery after the cycle is finished.
Wherein the change in the direct current resistance of the secondary battery and the volume of the generated gas are measured by the following methods, respectively:
(i) direct Current Resistance (DCR) test of secondary battery
When the battery is discharged to 50% SOC (state of charge, reflecting the residual capacity of the battery) at a specified temperature by 1C current, the current is increased to 4C and kept for 30s, the difference between the updated stable voltage and the original platform voltage is detected, and the ratio of the value to the 3C current value is the direct current resistance of the battery. And comparing the DCR after the cycle is ended with the DCR at the beginning of the cycle to obtain the increase rate of the DCR.
(ii) Volume change test of gas generated by secondary battery
Fixing the secondary battery with a string, completely soaking the secondary battery in water at 25 ℃, recording the weight difference before and after soaking, and converting the weight difference into the volume difference according to the density of the water at 25 ℃.
(2) Capacity recovery test of secondary battery at 60 deg.C
After aging treatment of examples and comparative examples, the activated batteries were charged to 4.3V at 25 ℃ with a current of 1C and were constant-voltage to a current of 0.05C. The secondary battery was placed in an environment at 60 ℃ for 60 days, and the capacity recovery rate was recorded for 60 days.
(3) Cycle test of secondary battery at 60 deg.C
After aging treatment of examples and comparative examples, the activated batteries were charged to 4.25V at 60 ℃ with a current of 1C, and were constant-voltage to a current of 0.05C, and then discharged to 3.0V at 1C, and the discharge capacity was recorded. And recording initial DCR of the battery after the first circle of discharge, then performing a cycle test until the discharge capacity of the battery is 80% of the first circle of capacity, and recording the DCR, the increase rate of the DCR and the gas production volume change of the battery after the cycle is finished.
Low temperature discharge test
The full-state battery after capacity separation was discharged to 3.0V at 25 ℃ at 1C, and the initial discharge capacity was recorded as DC (25 ℃). Then, the mixture was charged to 4.2V at 25 ℃ at a constant current and a constant voltage of 1C, and the current was cut off at 0.05C. The temperature is reduced to minus 20 ℃ and the mixture is kept for 4 hours, then the mixture is discharged to 3.0V at 1C, and the discharge capacity DC (-20 ℃) is recorded. The low-temperature discharge capacity retention rate was 100% DC (-20 ℃)/DC (25 ℃).
The corresponding electrolyte above was prepared according to the following examples:
example 1:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 12% of LiPF6 and 1.5% of LiPO which are calculated according to the total mass of the finished electrolyte2F21% LiFSI, 0.5% VC, 0.5% PS, 0.5% PST and 0.5% LiODFP, and uniformly mixing to obtain the electrolyte.
Comparative example 1:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 12% of LiPF6 and 1.5% of LiPO which are calculated according to the total mass of the finished electrolyte2F21% LiFSI, 2% VC and 0.5% PS, and uniformly mixing to obtain the electrolyte.
Comparative example 2:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 12% of LiPF6 and 1.5% of LiPO which are calculated according to the total mass of the finished electrolyte2F21% LiFSI, 0.5% VC, 0.5% PS and 1% PST, and uniformly mixing to obtain the electrolyte.
Comparative example 3:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 12% of LiPF6 and 1.5% of LiPO which are calculated according to the total mass of the finished electrolyte2F21% LiFSI, 0.5% VC, 0.5% PS and 1% LiODFP, and uniformly mixing to obtain the electrolyte.
The results of the electrical property tests of the lithium ion batteries of examples and comparative examples are shown in table 1, and the charge cut-off voltage of each lithium ion secondary battery was 4.4V. The results show that the method has the advantages of high yield,
TABLE 1 test results of electrical properties of different lithium ion batteries
Example 2:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 12% of LiPF6 and 1% of LiPO which are calculated according to the total mass of the finished electrolyte2F21% LiFSI, 1% LiTFSI, 1.5% DTD, 0.5% VC, 1% PS, 0.5% PST and 0.5% LiODFP, and uniformly mixing to obtain the electrolyte.
Example 3:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 6 parts of EMC, 1 part of DEC and 4 parts of PC/Add into a non-aqueous organic solvent, and adding 13% LiPF6 and 1% LiPO which are obtained according to the total mass of the finished electrolyte2F2、0.4％LiBF40.5% of DTD, 0.5% of VC, 1% of PS, 0.5% of PST and 0.5% of LiODFP, and uniformly mixing to obtain the electrolyte.
Example 4:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 13% of LiPF6 and 1% of LiPO which are calculated according to the total mass of the finished electrolyte2F23% of FEC, 1% of PS, 0.5% of PST and 0.5% of LiODFP, and uniformly mixing to obtain the electrolyte.
Comparative example 4:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 5 parts of EMC and 2 parts of DEC to obtain a non-aqueous organic solvent, and adding 13% of LiPF6 and 1% of LiPO which are calculated according to the total mass of the finished electrolyte2F23% of FEC, 1% of PS and 0.5% of LiODFP, and uniformly mixing to obtain the electrolyte.
Comparative example 5:
the preparation steps of the electrolyte are as follows:
mixing 3 parts of EC, 6 parts of EMC, 1 part of DEC and 4 parts of PC/Add into a non-aqueous organic solvent, and adding 13.5 percent LiPF6 and 1 percent LiPO which are calculated according to the total mass of the finished electrolyte2F2、0.4％LiBF40.5% of DTD, 0.5% of VC and 0.5% of PS are uniformly mixed to obtain the electrolyte.
The results of the electrical property tests of the lithium ion batteries of examples and comparative examples are shown in table 2, and the charge cut-off voltage of each lithium ion secondary battery was 4.4V. The results show that the method has the advantages of high yield,
TABLE 2 test results of electrical properties of different lithium ion batteries
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high-voltage non-aqueous electrolyte comprises electrolyte lithium salt, a non-aqueous organic solvent and an additive, and is characterized in that the additive comprises 1, 3-propylene sultone and lithium difluorobis (oxalato) phosphate;
wherein, the maximum empty molecular orbital level of the solvated lithium difluorobis (oxalato) phosphate is-7.45 eV and the minimum empty molecular orbital level is-0.18 eV according to the calculation of a B3LYP method in a density functional theory.
2. The high-voltage nonaqueous electrolyte solution of claim 1, wherein the additive further comprises one or more of 1, 3-propanesultone, fluoroethylene carbonate, ethylene sulfate, and vinylene carbonate.
3. The high-voltage nonaqueous electrolytic solution of claim 1, wherein the content of the electrolytic lithium salt is 10 to 20% by mass of the total mass of the electrolytic solution.
4. The high-voltage nonaqueous electrolytic solution according to claim 1, wherein the electrolyte lithium salt is one or more selected from lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium tetrafluoroborate.
5. The high-voltage nonaqueous electrolyte solution according to claim 1, wherein the nonaqueous organic solvent is one or more selected from a linear carbonate solvent, a cyclic carbonate solvent, a carboxylic acid ester solvent, and a fluorinated carbonate solvent.
6. The high-voltage nonaqueous electrolyte solution according to claim 5, wherein the linear carbonate-based solvent is one or more selected from ethyl methyl carbonate, dimethyl carbonate, and diethyl carbonate; the cyclic carbonate solvent is selected from one or more of ethylene carbonate and propylene carbonate; the carboxylic ester solvent is selected from one or more of ethyl acetate, ethyl propionate, methyl propionate, propyl butyrate and propyl acetate; the fluorinated carbonate solvent is selected from one or more of fluorinated ethylene carbonate, 1, 2-difluoroethylene carbonate, methyl trifluoroethyl carbonate and bis trifluoroethyl carbonate.
7. Use of the nonaqueous electrolytic solution according to any one of claims 1 to 6 for producing a lithium ion battery, wherein a charging voltage of the lithium ion battery is 5.5V or less.
8. A lithium ion battery, comprising: a positive electrode, a negative electrode, a separator between the positive electrode and the negative electrode, and the electrolyte of any one of claims 1 to 6;
the positive electrode includes a positive electrode active material;
the negative electrode comprises a negative current collector and a negative diaphragm arranged on the negative current collector, and the negative diaphragm comprises a negative active material, a negative conductive agent and a binder.
9. The lithium ion battery of claim 8, wherein the positive active material is selected from one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel manganate, lithium cobalt manganate, lithium manganese rich-based material and ternary positive material, and the ternary positive material has a structural formula of LiNi1-x-y-zCoxMnyAlzO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1.
10. The lithium ion battery of claim 8, wherein the negative active material is selected from one or more of artificial graphite, natural graphite, silicon-oxygen compound, silicon-based alloy and activated carbon; the negative electrode conductive agent is selected from one or more of acetylene black, conductive carbon black, carbon fiber, carbon nanotube and Ketjen black.
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| CN113823841A (en) * | 2021-10-29 | 2021-12-21 | 湖南法恩莱特新能源科技有限公司 | Electrolyte and preparation method and application thereof |
| CN115249840A (en) * | 2022-08-31 | 2022-10-28 | 远景动力技术(江苏)有限公司 | Electrolyte, electrochemical device and electronic device |
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| CN110265716A (en) * | 2019-06-13 | 2019-09-20 | 东莞维科电池有限公司 | A kind of lithium-ion battery electrolytes and lithium ion battery |
| CN111554898A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Negative electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113823841A (en) * | 2021-10-29 | 2021-12-21 | 湖南法恩莱特新能源科技有限公司 | Electrolyte and preparation method and application thereof |
| CN113823841B (en) * | 2021-10-29 | 2023-11-28 | 湖南法恩莱特新能源科技有限公司 | Electrolyte and preparation method and application thereof |
| CN115249840A (en) * | 2022-08-31 | 2022-10-28 | 远景动力技术(江苏)有限公司 | Electrolyte, electrochemical device and electronic device |
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