CN108232292B - Electrolyte for lithium ion battery - Google Patents
Electrolyte for lithium ion battery Download PDFInfo
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- CN108232292B CN108232292B CN201611158747.5A CN201611158747A CN108232292B CN 108232292 B CN108232292 B CN 108232292B CN 201611158747 A CN201611158747 A CN 201611158747A CN 108232292 B CN108232292 B CN 108232292B
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M10/42—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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention disclosesThe electrolyte for the lithium ion battery is provided, and comprises a solvent, lithium salt and an additive, wherein the mass fraction of the solvent is 97.5-99.5% and the balance of the additive is 100% of the total mass of the solvent and the additive; the concentration of the lithium salt is 1.0-1.15 mol/L; the additive is trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole ionic liquid. Compared with the prior art, the invention solves the problem that the ternary/graphite lithium ion battery is difficult to realize both high-temperature circulation and high-pressure circulation by adding the trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole ionic liquid into the conventional electrolyte, so that LiNi is enabled to bexCoyMnzO2The high-temperature cycle and the high-pressure cycle of the graphite lithium ion battery are improved, and the initial electrical property and the rate capability of the battery are better.
Description
Technical Field
The invention belongs to the technical field of new materials and electrochemistry, and particularly relates to an electrolyte for a lithium ion battery.
Technical Field
The lithium ion battery has the advantages of high energy density, good cycle performance, environmental protection, no pollution and the like, is widely applied and becomes a preferred power battery for electric vehicles and hybrid electric vehicles. With the gradual development of electric vehicles and hybrid electric vehicles, higher requirements are put forward on the performance of lithium ion batteries, and the lithium ion batteries are required to have the advantages of high energy density, good safety, good low-temperature performance and the like.
At present, the traditional lithium ion batteries, such as lithium manganate batteries, lithium iron phosphate batteries and ternary batteries, are difficult to meet the requirements of electric vehicles and hybrid electric vehicles on the lithium ion batteries due to respective defects. For ternary material lithium batteries, although the energy density is high, the cycle stability and safety are poor, so that it is necessary to develop new lithium ion batteries with high energy density, good cycle performance and good safety performance, and it is important to develop an electrolyte suitable for ternary material lithium batteries.
In recent years, it has been found that a reaction occurs at an interface between a positive electrode active material of a lithium ion battery and an electrolyte, which has an important influence on electrochemical performance, thermal stability, safety performance of the positive electrode active material of the lithium ion battery, and the like. Many relevant researches at home and abroad usually select excellent film forming additives and jointly use electrolytes such as ethylene sulfate, propane sultone, fluoroethylene carbonate and the like added into a lithium ion battery. However, the electrolyte containing the additive can show poor cycle performance and storage performance once used in a high-voltage (> 4.5V) system, and particularly the high-temperature cycle performance cannot meet the requirement. For example, chinese patent CN1612403A discloses a method of using a combination of fluoroethylene carbonate, ethylene carbonate and cyclic sulfate as an electrolyte of a lithium ion battery, which has good cycle performance and storage performance at a voltage of 4.2V or less, but cannot be used in a high voltage system; patent CN105428712A discloses that lithium trifluoromethanesulfonate and fluoroethylene carbonate are used as additives of lithium battery electrolyte, and the lithium battery with Si-based negative electrode active material has good cycle life. However, the cost of silicon negative electrode is much higher than that of graphite, and the electrolyte additive has poor cycle life performance for lithium battery whose negative active material is graphite, and is not economically suitable for lithium battery.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of poor high-temperature and high-pressure cycle performance of a lithium ion battery in the prior art, and provides an electrolyte for the lithium ion battery on the one hand, wherein the electrolyte comprises a solvent, a lithium salt and an additive, wherein the mass fraction of the solvent is 97.5-99.5% and the balance of the additive is 100% of the total mass of the solvent and the additive; the concentration of the lithium salt is 1.0-1.15 mol/L; the additive is trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole ionic liquid.
In some embodiments, the lithium salt is selected from one or a combination of two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis oxalate borate, lithium difluoro oxalate borate.
In some embodiments, the solvent includes a primary solvent and a secondary solvent, the primary solvent being selected from at least two of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC); the auxiliary solvent is fluoroethylene carbonate.
In some embodiments, the solvent composition is 20% to 50% of Ethylene Carbonate (EC), 20% to 40% of Propylene Carbonate (PC), 20% to 40% of dimethyl carbonate (DMC), 7.5% to 9.5% of fluoroethylene carbonate (FEC), the contents of each of which are percentages relative to the sum of the mass of the solvent and the additive.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte is the electrolyte for the lithium ion battery.
In some embodiments, the separator may be selected from polyester, polyethylene, polypropylene, Polytetrafluoroethylene (PTFE), polyimide having a non-woven structure, and in order to ensure heat resistance and mechanical strength of the separator, a separator including a ceramic component coating, having a single-layer or multi-layer structure, may also be used.
In some embodiments, the positive and negative electrodes include positive and negative current collectors and positive and negative active material layers formed on the positive and negative current collectors or on the positive and negative current collectors; the positive and negative electrode active material layers include positive and negative electrode active materials, an optional binder, and a conductive material.
In some embodiments, the positive electrode active material layer is composed of the following mass fractions: 91-94% of active substance ternary material LiNixCoyMnzO22-4% of conductive agent and 4-5% of binder, wherein the mass fraction is relative to the total mass of the positive electrode active material layer.
Preferably, the negative electrode active material layer is composed of the following substances in mass fraction: 88-92% of graphite, 2-4% of a conductive agent and 6-8% of a binder, wherein the mass fraction is relative to the total mass of the negative electrode active material layer.
The positive electrode active material LiNixCoyMnzO2Wherein x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.5, and z is more than or equal to 0.1 and less than or equal to 0.5.
The conductive agent is selected from one or more of natural graphite, artificial graphite, carbon black, acetylene black, carbon fiber, carbon nano tube, polyaniline and polythiophene.
The binder is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber and epoxy resin.
The negative electrode and the positive electrode may be manufactured by the following method: 1) mixing an active material, a conductive material, and a binder in a solvent to form an active material composition; 2) coating the composition on a current collector. The solvent includes N-methylpyrrolidone, etc., but the solvent is not limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through adding trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole ionic liquid into the conventional electrolyte, the problem that the ternary/graphite lithium ion battery is difficult to realize both high-temperature circulation and high-pressure circulation is solved, so that LiNi is used as the electrolytexCoyMnzO2The high-temperature cycle and the high-pressure cycle of the graphite lithium ion battery are improved, and the initial electrical property and the rate capability of the battery are better.
Drawings
FIG. 1: comparative example and example high temperature high pressure cycling test results
Definition of terms
The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
Unless expressly stated to the contrary, the temperatures recited herein are ranges of values. For example, "100 ℃ C" means that the temperature is in the range of 100 ℃. + -. 5 ℃.
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications based on the inventive concept herein will occur to those skilled in the art and are intended to be included within the scope of the present invention. The starting materials used in the examples are all commercially available.
Comparative example 1:
preparing lithium ion battery electrolyte:
in a glove box with the water content of less than 10ppm, uniformly mixing an organic solvent according to the mass fraction of 30% of Ethylene Carbonate (EC), 30% of Propylene Carbonate (PC), 30% of dimethyl carbonate (DMC), 8% of fluoroethylene carbonate (FEC) and 2% of 1, 3-Propane Sultone (PS), and adding electrolyte lithium salt LiPF6Preparing 1mol/L solution, fully stirring and uniformly mixing to prepare the electrolyte of the comparative example 1.
The lithium ion battery positive and negative electrode material comprises the following components:
the composition of the positive electrode material of the lithium ion battery (the mass fraction of the positive electrode material is 100 percent): 90% of ternary material LiNi0.5Co0.2Mn0.3O25% of conductive carbon black, 5% of polyvinylidene fluoride (PVDF).
The composition of the negative electrode material of the lithium ion battery (the mass fraction of the negative electrode material is 100 percent) is as follows: 89% graphite, 5% conductive carbon black, 6% polyvinylidene fluoride (PVDF).
The preparation method of the lithium ion battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, uniformly dispersing the raw materials in an N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on an aluminum foil of a positive current collector, and drying and rolling to obtain the positive electrode piece.
Preparing a negative electrode: weighing the raw materials according to the formula of the negative electrode, uniformly dispersing the raw materials in an N-methyl-2-pyrrolidone (NMP) solution to prepare a mixed slurry of the negative electrode, coating the slurry on a negative current collector aluminum foil, and drying and rolling to obtain a negative electrode plate.
The positive plate and the negative plate of the lithium ion battery prepared in the above way, electrolyte and other necessary battery components such as a PTFE diaphragm, a shell and the like are subjected to the processes of winding, casing, liquid injection, pre-punching, chemical forming, capacity grading and the like to obtain the 18650 type lithium ion battery. The lithium ion battery of comparative example 1 was prepared.
Comparative example 2:
preparing lithium ion battery electrolyte:
in a glove box with the moisture of less than 10ppm, an organic solvent is uniformly mixed according to the mass fraction of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 9.75 percent of fluoroethylene carbonate (FEC), 0.25 percent of 1, 1-Sulfuryl Diimidazole (SDM), and electrolyte lithium salt LiPF is added6Preparing 1mol/L solution, fully stirring and mixing uniformly to prepare the electrolyte of the comparative example 2.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Comparative example 3:
preparing lithium ion battery electrolyte:
in a glove box with the moisture of less than 10ppm, an organic solvent is uniformly mixed according to the mass fraction of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 9.0 percent of fluoroethylene carbonate (FEC), 1-dithiobisimidazole (SDM) and electrolyte lithium salt LiPF is added6Preparing 1mol/L solution and fully stirringThe mixture was mixed uniformly to obtain an electrolyte of comparative example 3.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Example 1:
preparing lithium ion battery electrolyte:
in a glove box with the water content of less than 10ppm, an organic solvent is uniformly mixed according to the mass fractions of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 9.5 percent of fluoroethylene carbonate (FEC) and 0.5 percent of trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole, and electrolyte lithium salt LiPF is added6A solution of 1mol/L was prepared and mixed well to prepare the electrolyte of example 1.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Example 2:
preparing lithium ion battery electrolyte:
in a glove box with the water content of less than 10ppm, an organic solvent is uniformly mixed according to the mass fractions of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 9.0 percent of fluoroethylene carbonate (FEC) and 1.0 percent of trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole, and electrolyte lithium salt LiPF is added6A solution of 1mol/L was prepared and mixed well to prepare the electrolyte of example 1.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Example 3:
preparing lithium ion battery electrolyte:
in a glove box with the water content of less than 10ppm, an organic solvent is uniformly mixed according to the mass fractions of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 8.5 percent of fluoroethylene carbonate (FEC) and 1.5 percent of trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole, and electrolyte lithium salt LiPF is added6A solution of 1mol/L was prepared and mixed well to prepare the electrolyte of example 1.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Example 4:
preparing lithium ion battery electrolyte:
in a glove box with the water content of less than 10ppm, an organic solvent is uniformly mixed according to the mass fractions of 30 percent of Ethylene Carbonate (EC), 30 percent of Propylene Carbonate (PC), 30 percent of dimethyl carbonate (DMC), 7.5 percent of fluoroethylene carbonate (FEC) and 2.5 percent of trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole, and electrolyte lithium salt LiPF is added6A solution of 1mol/L was prepared and mixed well to prepare the electrolyte of example 1.
The lithium ion battery components and the preparation method were the same as in comparative example 1.
Evaluation of Performance
The lithium ion batteries assembled in comparative examples 1 to 3 and examples 1 to 4 were evaluated for the following properties.
Performance evaluation 1:initial electrical and rate capability
The capacity, coulomb efficiency and multiplying power performance of the assembled lithium ion battery are tested by adopting a Land CT2001A battery test system, and the alternating current impedance EIS is tested by adopting a PGSTAT-30 electrochemical workstation, wherein the test method comprises the following steps:
at room temperature, the assembled lithium ion battery is charged to 4.5V for the first time by adopting a constant current of 0.2C, is charged at a constant voltage, has a cut-off current of 0.02C, and is then discharged to 2.75V by adopting a current of 0.2C, and the capacity, the coulombic efficiency CE and the alternating current impedance EIS are measured, and the result is shown in Table 1;
at room temperature, 0.2C, 0.5C, 1C, 2C, 4C, 8C current discharge was applied to the lithium ion battery charged to 4.5V, and the discharge capacity was measured, and the test results are shown in table 2.
TABLE 1
| Numbering | Initial capacity (mAh/g) | Coulomb efficiency (%) | AC impedance (m omega) |
| Comparative example 1 | 151.2 | 76.58 | 6.3 |
| Comparative example 2 | 152.5 | 74.65 | 6.5 |
| Comparative example 3 | 149.8 | 74.19 | 5.9 |
| Example 1 | 150.3 | 78.16 | 5.4 |
| Example 2 | 149.6 | 78.93 | 5.2 |
| Example 3 | 152.2 | 80.54 | 5.8 |
| Example 4 | 151.9 | 77.82 | 5.9 |
TABLE 2
From the test results in tables 1 and 2, it can be known that the initial electrical property and rate capability of the lithium ion battery obtained by using the electrolyte with trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole as an additive are better.
Performance evaluation 2:high temperature high pressure cycle life characteristics
And (3) carrying out 2.75-4.5V and 0.2C cyclic charge and discharge tests on the assembled lithium ion battery for 200 times by adopting a Land CT2001A battery test system at the temperature of 55 ℃ to obtain the discharge capacity of cyclic charge and discharge. The cycle performance test results are shown in fig. 1. As can be seen from fig. 1, the lithium ion battery obtained by using the electrolyte with trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole as an additive has better high-temperature and high-pressure cycle performance.
Claims (10)
1. The electrolyte for the lithium ion battery comprises a solvent, lithium salt and an additive, wherein the mass fraction of the solvent is 97.5-99.5% and the balance of the additive is 100%, and the concentration of the lithium salt is 1.0-1.15 mol/L;
the additive is characterized in that the additive is trifluoromethanesulfonic acid-3-methyl-1, 1' -sulfuryl diimidazole ionic liquid;
the anode active substance of the lithium ion battery is a ternary material, and the cathode active substance is graphite.
2. The electrolyte solution for a lithium ion battery according to claim 1, wherein the lithium salt is selected from one or a combination of two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate.
3. The electrolyte for a lithium ion battery according to claim 1, wherein the solvent comprises a primary solvent and an auxiliary solvent, and the primary solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; the auxiliary solvent is fluoroethylene carbonate.
4. The electrolyte for a lithium ion battery according to claim 3, wherein the solvent comprises 20 to 50% of ethylene carbonate, 20 to 40% of propylene carbonate, 20 to 40% of dimethyl carbonate and 7.5 to 9.5% of fluoroethylene carbonate, and the contents of the above components are percentages based on the sum of the mass of the solvent and the additive.
5. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte is the electrolyte for a lithium ion battery according to claim 1.
6. The lithium ion battery according to claim 5, wherein the separator is selected from one of polyester, polyethylene, polypropylene, polytetrafluoroethylene, polyimide having a non-woven structure, or a ceramic component-coated separator having a single-layer or multi-layer structure.
7. The lithium ion battery according to claim 5, wherein the positive and negative electrodes comprise positive and negative electrode current collectors and positive and negative electrode active material layers formed on the positive and negative electrode current collectors or on the positive and negative electrode current collectors; the positive and negative electrode active material layers include positive and negative electrode active materials.
8. The lithium ion battery according to claim 7, wherein the positive electrode active material layer is composed of the following substances in mass fraction: 91-94% of active substance ternary material LiNixCoyMnzO2，2～4% of conductive agent, 4-5% of binder, wherein the mass fraction is relative to the total mass of the positive electrode active material layer;
the negative electrode active material layer is composed of the following substances in mass fraction: 88-92% of graphite, 2-4% of a conductive agent and 6-8% of a binder, wherein the mass fraction is relative to the total mass of the negative electrode active material layer;
the positive electrode active material LiNixCoyMnzO2Wherein x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.5, and z is more than or equal to 0.1 and less than or equal to 0.5;
the conductive agent is selected from one or more of natural graphite, artificial graphite, carbon black, acetylene black, carbon fiber, carbon nano tube, polyaniline and polythiophene;
the binder is selected from one or more of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber and epoxy resin.
9. The lithium ion battery according to any one of claims 7 to 8, wherein the positive electrode and the negative electrode are produced by a method comprising: 1) mixing an active material, a conductive material, and a binder in a solvent to form an active material composition; 2) coating the composition on a current collector.
10. The lithium ion battery according to claim 9, wherein a solvent in the method for manufacturing the positive electrode and the negative electrode is N-methylpyrrolidone.
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| CN109244541B (en) * | 2018-11-23 | 2021-04-30 | 中国科学院过程工程研究所 | Electrolyte, lithium ion battery using electrolyte, and preparation method and application of lithium ion battery |
| CN109742448B (en) * | 2019-01-08 | 2019-12-13 | 江西理工大学 | Low-temperature electrolyte for lithium ion battery and preparation method thereof |
| CN109776423B (en) * | 2019-03-20 | 2020-12-08 | 厦门大学 | Double-imidazole-ring functional ionic liquid, preparation method thereof, electrolyte and lithium 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 |
| CN112467203A (en) * | 2019-09-09 | 2021-03-09 | 东莞市杉杉电池材料有限公司 | High-voltage-resistant non-aqueous electrolyte for lithium ion battery and ternary high-voltage lithium ion battery |
| CN111807935A (en) * | 2020-06-29 | 2020-10-23 | 国联汽车动力电池研究院有限责任公司 | Ionic liquid, ionic liquid electrolyte and application of ionic liquid electrolyte in battery |
| CN112467222B (en) * | 2020-10-23 | 2022-09-16 | 福建南平延平区南孚新能源科技有限公司 | Button secondary battery |
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| CN102723528B (en) * | 2012-06-06 | 2016-01-20 | 广州中科立新材料科技有限公司 | Amphion liquid electrolyte material and preparation thereof and application in lithium battery electrolytes |
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