CN111446495A - Non-combustible polymer electrolyte with high ion transport number and preparation method thereof - Google Patents

Non-combustible polymer electrolyte with high ion transport number and preparation method thereof Download PDF

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CN111446495A
CN111446495A CN202010198366.XA CN202010198366A CN111446495A CN 111446495 A CN111446495 A CN 111446495A CN 202010198366 A CN202010198366 A CN 202010198366A CN 111446495 A CN111446495 A CN 111446495A
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polymer electrolyte
metal salt
vinyl ether
carbonate
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陈茂
马明钰
赵宇澄
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Fudan University
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
    • C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • 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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention belongs to the technical field of polymer electrolytes, and particularly relates to a non-combustible polymer electrolyte with high ion migration number and a preparation method thereof. The polymer electrolyte of the invention takes vinyl fluoride and vinyl ether and derivatives thereof as polymerization monomers, wherein the vinyl fluoride can be chlorotrifluoroethylene, tetrafluoroethylene and hexafluoropropylene, and the vinyl ether monomers can be derivatives with a plurality of oxygen-containing functional groups with different numbers on side chains. The polymerization reaction is carried out under the condition of heating or illumination to obtain the polymer. The polymer electrolyte obtained by the invention has high ionic conductivity and high lithium ion transference number, and has incombustibility and excellent chemical stability. The method has the advantages of low monomer raw material cost, mild reaction conditions and suitability for industrial quantitative production.

Description

Non-combustible polymer electrolyte with high ion transport number and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer electrolytes, and particularly relates to a novel non-combustible polymer electrolyte with high ion migration number and a preparation method thereof.
Background
Metal ion batteries (such as lithium ion batteries) have the advantages of high energy density, long cycle life, high power density, no memory effect and the like, and are considered to be an energy storage device with the most application prospect. Currently, conventional metal-ion batteries use organic liquid electrolytes. However, the liquid electrolyte has safety problems of easy leakage, easy volatilization, flammability and the like, and the application of the battery in the fields of automobile power sources, electric vehicle energy sources and the like is seriously hindered. Compared with the traditional liquid electrolyte, the solid polymer electrolyte can fundamentally avoid the dangers of electrolyte leakage, combustion explosion and the like, has better safety and machinability, and can effectively inhibit the generation of metal dendrite. With the increasing demand for new energy in the fields of electric vehicles, unmanned aerial vehicles, personal portable devices, and the like, the research and development of high-performance solid polymer electrolytes have become a focus of attention of global researchers.
Research on polymer electrolytes dates back to 1973 for the first time, and Fenton et al found that mixing polyethylene oxide (PEO) with an alkali metal sodium salt can form an electrolyte with ionic conductivity (publication: Polymer.1973, 14,589). In 1992, the Armand project group has conducted intensive research on the ion transport mechanism of polymer electrolytes (journal: Electrochim. Acta.1992, 37, 1699-1701), however, PEO has low room temperature conductivity and poor machinability, which limits its application. The Feuillade group uses a cross-linked copolymer of vinylidene fluoride-hexafluoropropylene copolymer and polyacrylonitrile for a polymer electrolyte, and improves the electrochemical performance of the polymer electrolyte by doping propylene carbonate and electrolyte salt. Subsequently, Bellcore, USA, uses a polymer electrolyte membrane as a commercial lithium ion battery electrolyte (U.S. Pat. No. US6268088B 1), which provides a solution to the problems of leakage and burning of lithium ion batteries, and attracts much attention. However, solid polymer electrolytes have so far presented a number of problems to be solved, including: ionic conductivity at room temperature Low ion mobility, low processability of low molecular weight polymers, insufficient thermal stability of polymers, harsh polymerization conditions, and the like. In addition, the solid polymer electrolyte has poor interfacial compatibility, and in practical application, small molecules such as solvents, plasticizers and the like are often required to be added, so that the electrolyte still has the possibility of being flammable.
Fluoropolymers generally have excellent heat resistance, chemical resistance, durability, weatherability, and the like, and are indispensable key materials in the fields of military, aerospace, medical, electrical and electronics, and the like. The control of polymer crystallinity, solubility and electrochemical performance can be realized by controlling the main chain and side chain structure of the fluorine polymer (patent No. CN 103456909). Recent research results show that the fluoropolymer electrolyte has the advantages of non-flammability, high ion migration number and the like, and can reduce the concentration polarization of the electrolyte and increase the specific energy and specific power of the battery in the charging and discharging processes of the battery. Therefore, the fluoropolymer electrolyte shows wide application prospects in the field of new energy (publication: ACS Appl. Energy Mater.2018,1, 2, 483-494; patent numbers: CN 105914397A). However, the fluoropolymers currently available for use in electrolytes are not only very few in type, but also have low molecular weight, and have problems such as leakage and difficulty in processing into films. In addition, in order to improve the electrochemical performance, it is generally necessary to add organic small molecules such as a solvent and a plasticizer to the fluorine electrolyte, which poses a danger of flammability to the battery.
The fluorine-containing olefin monomer is a common industrial raw material and is used for producing fluoropolymer materials such as chlorotrifluoroethylene-ethylene copolymer (Halar) (patent number: CN 109722175A), tetrafluoroethylene-ethylene copolymer (Tefzel) (patent number: CN 110204969A; CN 110066610A) and the like on a large scale. The product is an alternating copolymer formed by starting from a fluorine-containing olefin monomer which is cheap and easy to obtain and an alkenyl ether. The polymer has the advantages of non-flammability, high ion migration number, high ion conductivity, processability and the like, and can be used as a high-performance solid polymer electrolyte. The fluorine polymer electrolyte meets the requirements of high capacity and high safety of the battery, and is suitable for mass production. With the increasing global demand of batteries, the invention has important significance in the fields related to new energy resources, such as portable electronic devices, electric vehicles, unmanned aerial vehicles and the like.
Disclosure of Invention
The invention aims to provide a novel non-flammable polymer electrolyte with high ion migration number and a preparation method thereof, the polymer is non-flammable, and the polymer electrolyte has high metal ion migration number, excellent electrochemical stability and thermal stability and higher conductivity under room temperature and heating conditions.
The invention adopts a free radical polymerization method, takes fluorine-containing ethylene, vinyl ether and derivatives thereof as polymerization monomers, and realizes the alternating copolymerization of the monomers in the presence of a solvent by a heating or illumination mode, wherein the vinyl ether monomers can have oxygen-containing flexible groups, and the polymer electrolyte with incombustible property and high metal ion migration number is prepared after adding a certain proportion of metal salt, and has the following structure formula (I):
Figure DEST_PATH_IMAGE001
Formula (I)
Wherein R1 is a chlorine atom, a fluorine atom or a trifluoromethyl group; x is alkyl with 2-12 carbon atoms or polyethylene glycol with 1-12 repeating units; r2 is hydrogen atom, chlorine atom, iodine atom, methyl group, ethyl group, isopropyl group, isobutyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group or 1, 3-dioxan-2-one.
The invention provides a preparation method of a non-flammable polymer electrolyte with high ion migration number, which comprises the following specific steps:
Step (1), alternating copolymerization of monomers;
The method A comprises the following steps: mixing a fluorine-containing ethylene monomer, a vinyl ether monomer, an initiator and a solvent by a heating method, and adding into a reaction bottle; calculated according to molar ratio, the monomer is initiator =1000 (1-100);
The method B comprises the following steps: mixing a fluorine-containing ethylene monomer, a vinyl ether monomer, a chain transfer agent, a photocatalyst and a solvent by a light irradiation method, and adding into a reaction bottle; according to the molar ratio, the monomer is chain transfer agent =1000 (1-100), and the photocatalyst used in the reaction process is 0.0001-10 mol% of the monomer; the reaction formula is as follows:
Figure 69866DEST_PATH_IMAGE002
Formula (II)
Step (2), after the reaction is finished, removing the solvent to obtain poly (vinyl fluoride- Alternating -vinyl ether) copolymers;
And (3) adding the copolymer obtained in the step (2) into metal salt and an additive, and completely mixing to obtain the solid polymer electrolyte.
In the step (1), the reaction solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, anisole, N,N-dimethylformamide, N,N-dimethylacetamide, N-one or more of methyl pyrrolidone, 5-fluoropropane, 5-fluorobutane, acetonitrile, dimethyl sulfoxide, ethyl acetate, toluene, xylene, supercritical carbon dioxide.
In step (1) of the present invention, the initiator in method a is one or more of azo compounds and organic peroxides. The chain transfer agent in the method B is one or more of a thioreagent, an organic nitrogen oxide, alkyl halide or perfluoroalkyl halide; the photocatalyst is one or more of organic micromolecular compounds taking perylene, pyrene, porphyrin, thiophene, phenothiazine and phenoxazine as frameworks, or one or more of metal organic complexes taking copper, ruthenium and iridium as cores.
In step (3) of the present invention, the metal salt is one or more of bis (trifluoromethyl) sulfonyl imide metal salt, bis (trifluoromethyl) sulfonic acid metal salt, bis (difluoro) sulfonyl imide metal salt, bis (pentafluoroethyl) sulfonyl imide metal salt, tris (trifluoromethyl) sulfonyl methyl metal salt, trifluoro-methanesulfonic acid metal salt, difluoro-oxalic acid metal salt, bis-oxalic acid metal salt, perchloric acid metal salt, tetrafluoro-boric acid metal salt, hexafluoro-arsenic metal salt and hexafluoro-phosphoric acid metal salt, wherein the metal salt may be lithium, sodium or potassium.
In the step (3), the additive is one or more of dimethylformamide, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, methyl formate, methyl acetate, 1, 2-dimethoxyethane, polyethylene glycol and polypropylene glycol.
In the step (1), the heating temperature of the heating method is minus 20-200 ℃; the illumination wavelength of the illumination method is 200-850 nm.
The fluorine-containing copolymer of the present invention can be applied to a metal ion battery as a polymer electrolyte. The metal ion battery comprises a lithium ion battery, a sodium ion battery and a potassium ion battery.
Experimental results show that the polymer electrolyte is successfully obtained by the method, and the polymer electrolyte is high in ion transference number, good in electrochemical stability and non-flammable after being used for the electrolyte of the metal ion battery. The monomer raw materials of the method are low in price and easy to obtain, and the synthesis method is simple and easy for mass production.
Drawings
FIG. 1 is a schematic diagram of a polymer electrolyte.
FIG. 2 is a schematic diagram of an EIS impedance spectrum of a polymer electrolyte at 100 degrees Celsius.
FIG. 3 is a graph showing the results of electrochemical performance tests on the transference number of lithium ions in example 3.
Fig. 4 is a graph showing the results of the conductivity test performed in example 3 at room temperature to 100 degrees celsius.
Detailed Description
The present invention is described in detail below with reference to some specific embodiments, which are only used for illustrating the present invention and are not used for limiting the scope of the present invention, and the preparation schemes in the examples are only preferred schemes, but the present invention is not limited to the preferred preparation schemes. For the same reaction, the reaction time or the reaction device is adjusted to realize the synthesis of polymers with different scales without changing the parameters of reaction conditions.
A first part: a poly (vinyl fluoride-vinyl ether) copolymer was synthesized.
Example 1: light-controlled alternating copolymerization of chlorotrifluoroethylene and tert-butyldimethylsilanethyleneglycol vinyl ether, with dimethyl carbonate as solvent, in a molar ratio of chlorotrifluoroethylene: tert-butyldimethylsilylethylene glycol vinyl ether = 3: 2. According to the molar ratio, (chlorotrifluoroethylene + tert-butyldimethylsilylethylene glycol vinyl ether): cyanomethyl diphenyl thiocarbamate: tris (2-phenylpyridine) iridium = 200: 1: 0.05, and the two monomers, chain transfer agent and photocatalyst were added to the reaction flask. And (3) carrying out liquid nitrogen cooling, vacuumizing, unfreezing and deoxidizing on the reaction solution circularly, repeating the steps for three times, sealing, and reacting for 24 hours under the illumination of an ultraviolet lamp. And dripping the reaction solution into methanol for precipitation for three times, and drying in vacuum until the weight is constant to obtain a light yellow solid. By passing 1The conversion of t-butyldimethylsilylethylene glycol vinyl ether was 95% by H NMR and the molecular weight of the polymer was 95% by GPC M n= 5.7× 104g/mol, molecular weight distribution M w/M n= 1.53. The spectral data are: 1HNMR（400 MHz，CDCl3）: 4.65-4.47（m，1H）， 3.88-3.51 （m，8H），3.05-2.56（m，2H），0.88（s，9H），0.04（s， 6H）。
Example 2: heating alternating copolymerization of chlorotrifluoroethylene and 4-ethyl-1, 3-dioxanyl-2-keto vinyl ether, taking dimethyl carbonate as a solvent, and calculating according to molar ratio, the weight ratio of chlorotrifluoroethylene: 4-ethyl-1, 3-dioxanyl-2-ketovinyl ether = 3: 2. (chlorotrifluoroethylene + 4-ethyl-1, 3-dioxanyl-2-ketovinyl ether): azobisisobutyronitrile = 200: 1. Vacuumizing the pressure-resistant reaction kettle, carrying out nitrogen circulation deoxidization, adding the two monomers and the initiator into a Schlenk bottle under the protection of nitrogen atmosphere, transferring the mixture into the pressure-resistant reaction kettle by using a sleeve, and reacting for 24 hours at the temperature of 60 ℃. And dripping the reaction solution into methanol for precipitation for three times, and drying in vacuum until the weight is constant to obtain a light yellow solid. By passing 1The conversion of 4-ethyl-1, 3-dioxan-2-one vinyl ether by H NMR was 94%, and the molecular weight of the polymer by GPC was found to be M n= 5.2× 104g/mol, molecular weight distribution M w/M n= 1.58。
A second part: a poly (chlorotrifluoroethylene: vinyl ether) polymer electrolyte is prepared.
Example 3: the specific implementation steps are as follows, dissolving the poly (chlorotrifluoroethylene + tert-butyldimethylsilyl ethylene glycol vinyl ether) copolymer in the reformed dimethyl carbonate, and according to the molar ratio, the poly (chlorotrifluoroethylene + tert-butyldimethylsilyl ethylene glycol vinyl ether) copolymer: and (3) adding the lithium bis (trifluoromethyl) sulfonyl imide = 1: 2 into the copolymer solution, uniformly stirring, and drying in a vacuum oven for 36 hours to obtain the polymer electrolyte.
Example 4: the specific implementation steps are as follows, dissolving the poly (chlorotrifluoroethylene + 4-ethyl-1, 3-dioxanyl-2-ketovinyl ether) copolymer in the redistilled dimethyl carbonate, and according to the molar ratio, the poly (chlorotrifluoroethylene + 4-ethyl-1, 3-dioxanyl-2-ketovinyl ether) copolymer: lithium bistrifluoromethylsulfonyl imide = 1: 5; and adding lithium bistrifluoromethylsulfonyl imide into the copolymer solution, uniformly stirring, and drying in a vacuum oven for 36 hours to obtain the polymer electrolyte.
And a third part: in this example, poly (vinyl fluoride: vinyl ether) polymer electrolytes were separately loaded into CR2032 symmetric cells and subjected to electrochemical impedance testing at room temperature to 100 degrees celsius. The method comprises the following specific steps:
(1) Preparation of polymer electrolyte: dissolving the copolymer product synthesized in example 1 and lithium bistrifluoromethylsulfonyl imide in an anhydrous tetrahydrofuran solvent, uniformly stirring the solution, heating to 100 ℃, and drying for 24 hours; then placing the mixture in a vacuum oven for drying for 36 hours, and removing the tetrahydrofuran solvent to obtain a light yellow solid;
(2) Preparation of a symmetrical battery: placing the polymer electrolyte between two lithium sheets in an argon atmosphere, adding a gasket and a positive and negative battery shell, and sealing by using a hydraulic machine;
(3) Heating to be tested: the sealed cells were equilibrated at 80 degrees celsius for 12 hours and electrochemical impedance tests were performed at various temperatures.
the electrochemical impedance spectrum measured in this example is shown in fig. 2, and the ionic conductivity and lithium ion migration number of the copolymer electrolyte are calculated as shown in fig. 3 and 4, the lithium ion migration number of the copolymer polymer electrolyte in the symmetric cell at room temperature is 0.6, and when the temperature reaches 100 ℃, the conductivity of the copolymer polymer electrolyte reaches 1.104 × 10 -4Scm-1. Compared to polyethylene oxide and polyvinylidene fluoride, poly (vinyl fluoride-vinyl ether) copolymers have lower ionic conductivity and higher lithium ion transport number, and are more electrochemically stable. In addition, a combustion test is carried out on the polymer electrolyte, which shows that the polymer electrolyte is not combustible at high temperature, and compared with the polyvinylidene fluoride electrolyte added with solvent and plasticizer micromolecules in a system, the polyvinylidene fluoride electrolyte has better thermal stability and safety.
The poly (vinyl fluoride-vinyl ether) polymer has the advantages of high ion migration number, high ionic conductivity, incombustibility, processability and the like, can be used as a high-performance solid polymer electrolyte, meets the requirements of high performance and large capacity of batteries, and can be applied to the fields of electric vehicles, electric appliance power devices and the like in the future.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (11)

1. A polymer electrolyte having a structure represented by the following formula (I):
Figure 854717DEST_PATH_IMAGE002
(I)
Wherein R is 1Is a chlorine atom, a fluorine atom or a trifluoromethyl group; x is alkyl with 2-12 carbon atoms or polyethylene glycol with 1-12 repeating units; r 2Is hydrogen atom, chlorine atom, iodine atom, methyl, ethyl, isopropyl, isobutyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl or 1, 3-dioxanyl-2-one.
2. The method for preparing the polymer electrolyte according to claim 1, comprising the steps of:
Step (1), alternating copolymerization of monomers;
The method A comprises the following steps: mixing a fluorine-containing ethylene monomer, a vinyl ether monomer, an initiator and a solvent by a heating method, and adding into a reaction bottle; the molar ratio of the monomers: initiator = 1000 (1-100);
The method B comprises the following steps: mixing a fluorine-containing ethylene monomer, a vinyl ether monomer, a chain transfer agent, a photocatalyst and a solvent by a light irradiation method, and adding into a reaction bottle; the molar ratio of the monomers: the chain transfer agent = 1000 (1-100), and the photocatalyst used in the reaction process is 0.001-10 mol% of the monomer; the reaction formula is as follows:
Figure 568596DEST_PATH_IMAGE004
(II)
Step (2), after the reaction is finished, removing the solvent to obtain poly (vinyl fluoride- Alternating -vinyl ether) copolymers;
And (3) adding metal salt and an additive into the copolymer obtained in the step (2), and completely mixing to obtain a solid fluorine-containing copolymer which can be used as an electrolyte.
3. The method according to claim 2, wherein the solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, anisole, or a mixture thereof, N,N-dimethylformamide, N,N-dimethylacetamide, N-one or more of methyl pyrrolidone, 5-fluoropropane, 5-fluorobutane, acetonitrile, dimethyl sulfoxide, ethyl acetate, toluene, xylene, supercritical carbon dioxide.
4. The method for preparing a polymer electrolyte according to claim 2, wherein in the step (1), the initiator is one or more of an azo compound and an organic peroxide.
5. The method for preparing a polymer electrolyte according to claim 2, wherein in the step (1), the method B, the chain transfer agent is one or more of a thioreagent, an organic nitrogen oxide, an alkyl halide or a perfluoroalkyl halide.
6. The method for preparing a polymer electrolyte according to claim 2, wherein in the step (1), in the method B, the photocatalyst is one or more of organic small molecular compounds with perylene, pyrene, porphyrin, thiophene, phenothiazine and phenoxazine as a skeleton, or one or more of metal organic complexes with copper, ruthenium and iridium as cores.
7. The method for producing a polymer electrolyte according to claim 2, wherein in the step (3), the metal salt is one or more of a bistrifluoromethylsulfonyl imide metal salt, a bisdifluorosulfonyl imide metal salt, a bistrifluoroethylsulfonyl imide metal salt, a tritrifluoromethylsulfonyl imide metal salt, a trifluoromethanesulfonic acid metal salt, a difluorooxalato borate metal salt, a bisoxalato borate metal salt, a perchlorato borate metal salt, a tetrafluoroborato borate metal salt, a hexafluoroarsenate metal salt, and a hexafluorophosphate metal salt, wherein the metal salt is lithium, sodium, or potassium.
8. The method of claim 2, wherein in the step (3), the additive is one or more selected from the group consisting of dimethylformamide, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, methyl formate, methyl acetate, 1, 2-dimethoxyethane, polyethylene glycol, and polypropylene glycol.
9. The method for preparing a polymer electrolyte according to claim 2, wherein in the step (1), the heating temperature is minus 20 to 200 ℃; the illumination wavelength of the illumination method is 200-850 nm.
10. Use of a polymer electrolyte as claimed in claim 1 in a metal-ion battery.
11. Use of the polymer electrolyte according to claim 10 in a metal-ion battery which is a lithium-ion battery, a sodium-ion battery or a potassium-ion battery.
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JP2001135353A (en) * 1999-11-02 2001-05-18 Nippon Mektron Ltd Electrolyte gel for lithium ion battery
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CN110357992A (en) * 2019-07-09 2019-10-22 复旦大学 A kind of fluoropolymer-containing preparation method of super high molecular weight

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Application publication date: 20200724