CN112310472B - Solid electrolyte membrane, preparation method and battery - Google Patents
Solid electrolyte membrane, preparation method and battery Download PDFInfo
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- CN112310472B CN112310472B CN202011221168.7A CN202011221168A CN112310472B CN 112310472 B CN112310472 B CN 112310472B CN 202011221168 A CN202011221168 A CN 202011221168A CN 112310472 B CN112310472 B CN 112310472B
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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 present invention provides a solid electrolyteA membrane, a method of making the same, and a battery comprising the same. The solid electrolyte membrane comprises a base film and a first polyethylene oxide film laminated on one surface of the base film, wherein only the surface facing outwards of the first polyethylene oxide film comprises-C2H4‑xFxAn O-structure, wherein x is an integer from 1 to 4. According to the invention, the surface of the PEO membrane is fluorinated, so that the oxidation resistance of the electrolyte membrane is improved and the service life of the battery is prolonged on the premise of minimizing the overall influence on the lithium ion transmission performance of the membrane; meanwhile, the fluoride layer has a strong bonding effect on the surface of the pole piece, so that the interface impedance of the electrolyte membrane and the pole piece can be improved, and the cycle performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a solid electrolyte membrane, a preparation method thereof and a battery comprising the solid electrolyte membrane.
Background
Polyethylene oxide (PEO) is widely used as a solid electrolyte membrane of a lithium ion battery because it has an optimal lithium ion transport property. However, PEO films are oxidatively decomposed when in contact with a positive electrode material having a potential higher than 3.8V for lithium. Current protective measures for PEO are: (1) the method can affect the creep property of PEO chains and reduce the lithium ion transmission performance of the whole electrolyte membrane; (2) the isolation coating is added on the surface of the PEO film, and due to the performance limitation of the isolation coating, the negative effect on the electrolyte film is large; (3) the surface of the anode is added with a lithium ion conductor coating, and the coating needs to face the stability problem because the anode material has scale strain in the charging and discharging processes.
Therefore, it is highly desirable to find a solution to improve the stability of PEO membranes.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks, the present invention provides a solid electrolyte membrane, a method of preparing the same, and a battery including the solid electrolyte membrane.
One aspect of the present invention provides a solid electrolyte membrane comprising a base film and a first polyethylene oxide film laminated on one surface of the base film, the first polyethylene oxide film comprising-C only on the surface facing the outside2H4-xFxAn O-structure, wherein x is an integer from 1 to 4.
Another aspect of the present invention provides a method of preparing a solid electrolyte membrane, including: providing a base film; forming a first polyethylene oxide film on one surface of the base film; and fluorinating the surface of the first polyethylene oxide film facing outward to form-C on the surface2H4-xFxAn O-structure, wherein x is an integer from 1 to 4.
Another aspect of the present invention also provides a battery including the above solid electrolyte membrane.
According to the invention, the surface fluorination treatment is carried out on the PEO membrane, so that the oxidation resistance of the electrolyte membrane is improved and the service life of the battery is prolonged on the premise of minimizing the overall influence on the lithium ion transmission performance of the membrane; meanwhile, the fluoride layer has a strong bonding effect on the surface of the pole piece, so that the interface impedance of the electrolyte membrane and the pole piece can be improved, and the cycle performance of the battery is improved.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic view of a solid electrolyte membrane of the present invention.
FIG. 2 is a schematic view of a fluorination process according to an embodiment of the present invention.
Fig. 3 is a charge and discharge graph of a lithium ion battery assembled with the solid electrolyte membranes of examples 1 to 3 and comparative examples 1 to 2.
Wherein the reference numerals are as follows:
1-a base film; 2-a first polyethylene oxide film; 3-a second polyethylene oxide film; 4-an electrolytic cell; 5-Olah reagent solution; 6-a nickel anode; 7-pair rollers; 8-composite film
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The solid electrolyte membrane of the present invention comprises a base film and a first polyethylene oxide film laminated on one surface of the base film, wherein only the surface of the first polyethylene oxide film facing outward comprises-C2H4-xFxO-structure, where x is an integer from 1 to 4, i.e., x can be 1, 2, 3, 4. The surface fluorination treatment is carried out on the PEO film, the interior fluorination treatment is not carried out, the transmission performance of lithium ions in the PEO film cannot be influenced, meanwhile, the fluorination layer has a strong bonding effect on the surface of the positive plate or the negative plate, the interface impedance of the electrolyte film and the positive plate or the negative plate can be improved, and the cycle performance of the battery is improved. In addition, for a PEO film as a solid electrolyte, point contact with the surface of the positive electrode material on the positive electrode sheet is common in the battery, and therefore the present invention introduces a passivation group (-C) only on the surface of the film by subjecting the PEO film to surface fluorination treatment of the positive electrode face (as shown in fig. 1)2H4-xFxO-structure) which can improve the oxidation resistance of the electrolyte membrane and improve the battery life with minimal overall impact on the membrane lithium ion transport performance.
In an alternative embodiment, the first polyethylene oxide film has a F content of 50 to 500ppm based on the total mass of the first polyethylene oxide film. It is understood by those skilled in the art that the compatibility between the solid electrolyte membrane and the positive electrode sheet can be improved as long as the surface of the first polyethylene oxide film contains F, and the limitation of the lower limit of the first polyethylene oxide film to 50ppm is only the lower limit in the preferred embodiment, and it is not intended to illustrate that less than 50ppm cannot achieve the object of the present invention. The larger the F content in the first polyethylene oxide film, the larger the influence on the lithium ion transport property, and the upper limit is preferably 500 ppm. Any suitable value between 50-500ppm can be selected by the skilled person according to the actual need, such as, but not limited to, 50ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500ppm, etc.
In an alternative embodiment, the other surface of the base film is further provided with a second polyethylene oxide film, and the surface of the second polyethylene oxide film does not include-C2H4-xFxAn O-structure. The surface of the PEO film on only one side of the solid electrolyte membrane comprises the passivating group, so that the electrochemical stability, the interface compatibility and the ionic conductivity are considered.
In an alternative embodiment, the first polyethylene oxide film and the second polyethylene oxide film further comprise a lithium salt and a lithium ion conductor. The lithium salt and lithium ion conductor may be lithium salts or lithium ion conductors commonly used in lithium ion batteries, for example, but not limited to, the lithium salt may be LiTFSI, LiFSI, LiPF6And the lithium ion conductor may be one or more of a garnet-type ion conductor, a NASICON-based ion conductor, a LISCON-based ion conductor, and the like. The content of lithium salt in the film is 10-30 wt% of the total mass of the film, i.e. the content is selected by those skilled in the art according to the actual requirement, such as but not limited to 10%, 15%, 20%, 25%, 30% and so on. The content of the lithium ion conductor in the film is 10-30 wt% of the total mass of the film, i.e. the content is selected by the skilled person according to the actual requirement, such as but not limited to 10%, 15%, 20%, 25%, 30% and so on. The weight average molecular weight of the PEO in the first polyethylene oxide film and the second polyethylene oxide film can be appropriately selected according to the actual situation, that is, PEO having a weight average molecular weight of 40 to 60 ten thousand, which is suitable as a solid electrolyte of a lithium ion battery, can be selected.
The base film of the solid electrolyte membrane may be any base film suitable for use as a battery separator, such as a PE film, a PP film, a composite film thereof, and the like.
The solid electrolyte membrane of the present invention can be prepared by a method comprising: providing a base film; forming a first polyethylene oxide on a surface of a base filmA film; and fluorinating the surface of the first polyethylene oxide film facing outward to form-C on the surface2H4-xFxAn O-structure, wherein x is an integer from 1 to 4.
Thereafter, a second polyethylene oxide film may be further formed on the other surface of the base film.
In an alternative embodiment, the fluorination process may be an electrochemical fluorination process. The electrochemical fluorination treatment is to utilize a nickel anode, take a solution containing a fluorination reagent as an electrolyte, and generate high-valence nickel fluoride with strong fluorination capacity during electrolysis, wherein the high-valence nickel fluoride is used for fluorinating a solid electrolyte membrane to be treated. Fluorination reagents used in electrochemical fluorination processes include, but are not limited to, pure HF, Olah's reagent (pyridinium polyhydrofluoride), HF-ether complexes (e.g., 2 HF-Me)2O, etc.), Et3N·3HF，Bu4N·H2F3And so on. Preferably, the fluorination reagent is an Olah reagent that is relatively mild in the electrochemical fluorination process. The reaction process of the electrochemical fluorination treatment according to the present invention is described below by taking the Olah reagent as an example:
NiF3+F- =NiF4+e-；
nxNiF4+(C2H4O)n=nxNiF3+(C2H4-xFxO)n+nxH++nxe-。
in other embodiments, the fluorination treatment may be any other suitable method that can form the passivating group on the surface.
The present invention also includes a battery using the above solid electrolyte membrane, the battery including a positive electrode sheet, the first polyethylene oxide film being opposed to the positive electrode sheet. Namely, the surface including the side of the passivation group is directly contacted with the positive plate, thereby overcoming the oxidation of PEO by the positive material, simultaneously minimizing the ionic conductivity and prolonging the service life of the battery.
In one embodiment, a battery using the above solid electrolyte membrane includes a cell unit formed by laminating a solid electrolyte membrane-a positive electrode sheet-a solid electrolyte membrane-a negative electrode sheet, wherein the two solid electrolyte membranes are the above solid electrolyte membranes, and the two solid electrolyte membranes are respectively opposite to the positive electrode sheets and the first polyethylene oxide membrane. The battery can be formed by laminating the battery cell units.
In other embodiments, the battery cell may also be a winding battery cell. Or a laminated cell, namely a solid electrolyte membrane is folded in a Z shape to separate a positive plate and a negative plate. It will be understood by those skilled in the art that the arrangement of the cells is not limited to the above-described manner, and may be any appropriate manner as long as the first polyethylene oxide film of the solid electrolyte membrane is opposite to the positive electrode tab to achieve the object of the present invention.
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
Example 1
Dissolving PEO (MW =400000) in DMF/acetonitrile (mass ratio of 1:2) to obtain a 20wt% glue solution, adding lithium salt (LiTFSI) and lithium ion conductor (LLZTO), stirring uniformly, coating on the A surface of a base film 1 (shown in figure 1), and drying to obtain a PEO coating with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
The PEO coating of the prepared composite membrane was subjected to an electrochemical fluorination treatment as shown in fig. 2. The prepared composite membrane 8 is partially immersed into an Olah reagent solution 5 through a pair of rollers 7 with nickel plated on the surface, and the electrolytic bath 4 is made of polytetrafluoroethylene. Olah reagent is C5H5N.HF (pyridinium polyhydrofluoride) with an HF content of 70%. The composite film 8 is close to the nickel anode 6 at the roller pair part. 5V voltage and 0.5A current are applied in the electrolytic bath 4, the electrolytic bath is slowly rotated at the rotating speed of 0.2m/min, and the A surface of the composite membrane 8 generates electrochemical fluorination reaction near the nickel anode 6. Thereby fluorinating the PEO coating to form a first polyethylene oxide film 2. And cleaning the composite membrane, removing residual HF and solvent, and drying for later use. As a result, the content of F in the first polyethylene oxide film 2 was found to be 87ppm based on the total mass of the first polyethylene oxide film 2.
Dissolving PEO (MW =400000) in DMF/acetonitrile (weight ratio of 1:2) to form 20wt% glue solution, adding lithium salt and lithium ion conductor, stirring uniformly, coating on the B surface of the base film 1, and drying to form a second polyethylene oxide film 3 with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
Example 2
The preparation procedure was the same as in example 1 except that the electrochemical fluorination treatment was different from that in example 1. The electrochemical fluorination treatment process in this example is as follows: a voltage of 5V and a current of 1A were applied to the electrolytic bath, and the film was slowly rotated at a rotation speed of 0.2m/min to obtain a first polyethylene oxide film 2 having an F content of 142 ppm.
Example 3
The preparation procedure was the same as in example 1 except that the electrochemical fluorination treatment was different from that in example 1. The electrochemical fluorination treatment process in this example is as follows: a voltage of 5V and a current of 3A were applied to the electrolytic cell, and the cell was slowly rotated at a rotation speed of 0.15m/min to obtain a PEO film having an F content of 442 ppm.
Comparative example 1
Dissolving PEO (MW =400000) in DMF/acetonitrile (mass ratio of 1:2) to obtain 20wt% glue solution, adding lithium salt and a lithium ion conductor, uniformly stirring, coating on the surface A of the base film, and drying to obtain a coating with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
Dissolving PEO (MW =400000) in DMF/acetonitrile (mass ratio of 1:2) to obtain 20wt% glue solution, adding lithium salt and a lithium ion conductor, uniformly stirring, coating on the B surface of a base film, and drying to obtain a coating with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
Comparative example 2
PEO (MW =400000) powder was placed in an empty PTFE cartridge, immersed in Olah reagent solution, next to a nickel anode. A voltage of 5V and a current of 0.5A are applied to the electrolytic bath 4, the PEO powder in the box is stirred slowly by a nickel rod to help the PEO powder to react with free F generated near the nickel anode for 5min, fluorinated PEO powder is obtained, and the fluorinated PEO powder is dried to remove residual solvent and HF.
Dissolving fluorinated PEO (MW =400000) in DMF/acetonitrile (mass ratio of 1:2) to obtain 20wt% glue solution, adding lithium salt and a lithium ion conductor, uniformly stirring, coating on the surface A of a base film, and drying to obtain a coating with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
Dissolving fluorinated PEO (MW =400000) in DMF/acetonitrile (mass ratio of 1:2) to obtain 20wt% glue solution, adding lithium salt and a lithium ion conductor, uniformly stirring, coating on the B surface of a base film, and drying to obtain a coating with the thickness of 12 μm for later use. Wherein the ratio of PEO: and (3) LiTFSI: LLZTO =5:2:3 (mass ratio).
The solid electrolyte membranes prepared in examples 1 to 3 and comparative examples 1 to 2 were assembled into lithium ion batteries, and then the assembled lithium ion batteries were subjected to performance tests.
Dissolving a binder PVDF (polyvinylidene fluoride) in non-aqueous NMP (N-methyl pyrrolidone), adding negative active material artificial graphite and conductive agents (KS-6 and SP), and fully mixing to prepare slurry, wherein the slurry comprises the following components: artificial graphite: KS-6: SP: PVDF =91:0.5:3.5:5 (mass ratio). And then, uniformly coating the obtained slurry on a copper foil with the thickness of 20 microns, baking and drying at the temperature of 120 ℃, and rolling to obtain the negative pole piece.
Dissolving binder PVDF in non-aqueous solvent NMP, adding positive active material NCM (ternary positive material, LiNi)0.5Co0.2Mn0.3O2) And acetylene black as a conductive agent, and fully mixing to prepare slurry, wherein the slurry comprises the following components: LiNi0.5Co0.2Mn0.3O2Acetylene black and PVDF in a ratio of 91:5:4 (mass ratio). Then, the obtained slurry was uniformly coated on an aluminum foil with an areal density of 170g/m2And baking and drying at 120 ℃, and rolling to obtain the anode piece.
Mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) according to the volume ratio of 1:1:1 to obtain an organic solvent to form an electrolyte, and then fully drying lithium salt LiPF6Dissolving the mixture in the mixed organic solvent to prepare electrolyte with the lithium salt concentration of 1 mol/L.
The solid electrolyte membranes prepared in examples 1 to 3 and comparative examples 1 and 2 were placed in the positive electrode tab and the negative electrode tab, respectively, to assemble a monolithic battery with a design capacity of 70mAh, and an electrolyte was injected, wherein the electrolyte injection coefficient was 1.8. The batteries were formed by vacuum sealing, standing, formation, shaping, and the like, and were referred to as M1 to M3 and N1 to N2, respectively. Wherein the surface of the first polyethylene oxide film 2 of the solid electrolyte membrane in examples 1 to 3 faces the positive electrode sheet side, and the surface of the fluorine-containing polyethylene oxide film of the solid electrolyte membrane in comparative example 2 faces the positive electrode sheet.
And carrying out 25 ℃ electrochemical performance test on the assembled batteries M1-M3 and N1-N2. The batteries of M1-M3 and N1-N2 are tested in an environment of 25 ℃, constant current and constant voltage charging is carried out firstly, the batteries of 0.1C are charged to 4.25V at constant current and constant voltage, the batteries of 0.05C are cut off, then constant current discharging is carried out, the batteries of 0.1C are discharged to 3V, and a first charge-discharge capacity-voltage curve is shown in figure 3; the capacity retention of the obtained battery was shown in table 1 after 100 cycles under the above charge and discharge conditions.
TABLE 1
Comparing the curves of the cells M1-M3, N2 and N1 in fig. 3, it can be seen that the fluorination of the solid electrolyte membrane improves the interface compatibility between the electrolyte membrane and the positive electrode, thereby increasing the first charge-discharge capacity of the cell. Comparing the curves of the cells M1 to M3 and N2 in fig. 3, it can be seen that if the solid electrolyte membrane is fully fluorinated, the fluorine content is too high, which affects the lithium ion transport and thus the capacity performance of the cell, while if the fluorination treatment is performed only on the surface of the solid electrolyte membrane opposite to the positive electrode, the fluorination treatment is not performed inside the electrolyte membrane, which improves the compatibility between the electrolyte membrane and the positive electrode interface, and does not affect the lithium ion transport, thus the capacity is fully exerted.
Comparing the capacity retention rates of the M1-M3, N2 and N1 batteries in Table 1 at 100 cycles, the solid electrolyte membrane without fluorination treatment is decomposed after 10 cycles to cause short circuit of positive and negative electrodes, and the capacity of the battery is reduced to 0. The solid electrolyte membrane is fluorinated to improve the interface compatibility of the electrolyte membrane and the anode, improve the oxidation of the surfaces of the electrolyte membrane and the anode and improve the cycle performance of the battery. If the solid electrolyte membrane is subjected to full fluorination treatment, the transmission of lithium ions is affected by the excessively high fluorine content, so that the capacity exertion of the battery is affected, and the cycle performance of the battery is affected; and only the surface of the solid electrolyte opposite to the positive electrode is subjected to fluorination treatment, and the interior of the electrolyte membrane is not subjected to fluorination treatment, so that the interface compatibility between the electrolyte membrane and the positive electrode is improved, the oxidation problem of the surfaces of the electrolyte membrane and the positive electrode is improved, the transmission of lithium ions is not influenced, the capacity is fully exerted, and the cycle performance is remarkably improved.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A solid electrolyte membrane comprising a base film and a first polyethylene oxide film provided on one surface of the base film, wherein only the surface of the first polyethylene oxide film facing outward comprises-C2H4-xFxAn O-structure, wherein x is an integer from 1 to 4;
the content of F in the first polyethylene oxide film accounts for 50-500ppm of the total mass of the first polyethylene oxide film;
the other surface of the base film is also provided with a second polyethylene oxide film, and the second polyethylene oxide film does not comprise the-C2H4-xFxAn O-structure.
2. The solid electrolyte membrane according to claim 1, wherein the first polyethylene oxide film and/or the second polyethylene oxide film further comprises a lithium salt and a lithium ion conductor.
3. The solid electrolyte membrane according to claim 2, wherein the lithium salt is LiTFSI, LiFSI, LiPF6The content of the lithium salt accounts for 10-30% of the total mass of the first polyethylene oxide film or the second polyethylene oxide film.
4. The solid electrolyte membrane according to claim 2, wherein the lithium ion conductor is one or more of a garnet-type ion conductor, a NASICON-based ion conductor, and a LISCON-based ion conductor, and the content of the lithium ion conductor is 10 to 30% of the total mass of the first polyethylene oxide film or the second polyethylene oxide film.
5. A method for producing a solid electrolyte membrane, characterized by comprising:
providing a base film;
forming a first polyethylene oxide film on one surface of the base film;
fluorinating the surface of the first polyethylene oxide film facing outward to form-C on the surface2H4-xFxAn O-structure, wherein x is an integer from 1 to 4; and
and forming a second polyethylene oxide film on the other surface of the base film.
6. The production method according to claim 5, wherein the fluorination treatment is an electrochemical fluorination treatment.
7. A battery comprising the solid electrolyte membrane according to any one of claims 1 to 4.
8. The battery of claim 7, further comprising a positive electrode tab, wherein the first polyethylene oxide film is opposite the positive electrode tab.
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| CN113346132B (en) * | 2021-05-24 | 2023-03-10 | 上海大学 | Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof |
| CN114512715A (en) * | 2022-01-20 | 2022-05-17 | 贵阳学院 | Polyoxyethylene-based solid electrolyte, preparation method thereof and lithium ion battery |
| CN114566702B (en) * | 2022-02-24 | 2023-05-30 | 华中科技大学 | Sandwich integrated all-solid-state polymer electrolyte membrane, preparation method and application thereof |
| CN116178698B (en) * | 2023-04-27 | 2024-03-08 | 北京宇极科技发展有限公司 | Fluorinated modified polyether, solid electrolyte membrane, preparation method of solid electrolyte membrane and energy storage battery |
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| CN105684207A (en) * | 2013-11-05 | 2016-06-15 | 索尼公司 | Battery, separator, electrode, paint, battery pack, electronic apparatus, electric vehicle, electricity storage device, and power system |
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| CN111370761A (en) * | 2020-03-25 | 2020-07-03 | 中航锂电技术研究院有限公司 | PEO film, preparation method thereof and solid-state battery |
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| CN105684207A (en) * | 2013-11-05 | 2016-06-15 | 索尼公司 | Battery, separator, electrode, paint, battery pack, electronic apparatus, electric vehicle, electricity storage device, and power system |
| CN109326822A (en) * | 2018-11-05 | 2019-02-12 | 珠海光宇电池有限公司 | A kind of preparation method and lithium ion battery of all solid state fluoropolymer electrolyte film |
| CN111370761A (en) * | 2020-03-25 | 2020-07-03 | 中航锂电技术研究院有限公司 | PEO film, preparation method thereof and solid-state battery |
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