CN113707935B - Polyfluorinated polymer solid electrolyte material and preparation method thereof - Google Patents
Polyfluorinated polymer solid electrolyte material and preparation method thereof Download PDFInfo
- Publication number
- CN113707935B CN113707935B CN202110946301.3A CN202110946301A CN113707935B CN 113707935 B CN113707935 B CN 113707935B CN 202110946301 A CN202110946301 A CN 202110946301A CN 113707935 B CN113707935 B CN 113707935B
- Authority
- CN
- China
- Prior art keywords
- polymer
- solid electrolyte
- polyfluorinated
- lithium
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the field of preparation and application of solid electrolyte, and particularly provides a polymer solid electrolyte material containing polyfluorinated groups and a preparation method thereof. The polymer solid electrolyte prepared by the invention has high ion conductivity and wide electrochemical activity window, can be compatible with lithium metal cathodes, and can be applied to solid batteries prepared from various anode materials. The solid electrolyte main body prepared by the invention is obtained by copolymerizing dodecafluoroheptyl methacrylate and methyl methacrylate, and has mild reaction conditions and easy realization; when the polymer main body is blended with lithium salt and plasticizer, the prepared polymer solid electrolyte has good chemical stability, shows high ionic conductivity in a wide temperature range, and reaches 2.5X10 at 30 DEG C ‑4 S·cm ‑1 The electrochemical window is above 4.7V. When LiFePO is used 4 When the NCM811 anode material is used for preparing the lithium metal all-solid-state battery, the initial specific discharge capacity respectively reaches 163.2mAh g ‑1 And 211.7mAh g ‑1 。
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a solid polymer solid electrolyte in a lithium ion battery and a preparation method thereof, and particularly provides a polyfluorinated polymer solid electrolyte material supported by a glass fiber porous membrane and a preparation method thereof.
Background
Along with the continuous promotion of the society on the modernization process, the demand for energy sources is also increasing; the high energy density and the power density of the lithium ion battery ensure the importance of the lithium ion battery in the field of energy storage, however, the electrolyte used in the lithium ion battery at the present stage is often liquid organic electrolyte with combustibility, and great potential safety hazard exists in the actual use process.
The solid polymer solid electrolyte is used for replacing the traditional electrolyte, so that the safety problem of the lithium ion battery in use can be solved radically; besides safety, the solid polymer solid electrolyte also has the advantages of high voltage resistance, easy processing and forming, light weight, high strength, low reactivity with electrode materials, good viscoelasticity and the like, and is considered to be a lithium ion battery electrolyte with very good development prospect. Polymer solid electrolytes are generally classified into all-solid polymer solid electrolytes and gel polymer solid electrolytes according to whether a liquid plasticizer is added or not. In the absence of a liquid plasticizer, all-solid polymer solid electrolyte conducting lithium ions is primarily related to the interactions of lithium ions with the polymer segments, and the ability of the polymer segments to move, primarily in the amorphous regions of the polymer; however, the polymer tends to have strong crystallinity, so that the free volume available for lithium ion migration is small, and the ionic conductivity is low although the electrochemical stability and the stability to an electrode are good. In gel polymer solid electrolyte, lithium ion migration is mainly carried out in electrolyte, and the polymer only serves as a framework for supporting; due to the presence of electrolyte plasticizers, gel polymer solid electrolytes tend to have higher ionic conductivity, but are not mechanically strong and have no way to avoid potential safety hazards due to electrolyte decomposition.
Disclosure of Invention
The invention aims at providing a polyfluorinated polymer solid electrolyte material and a preparation method thereof, aiming at the defects of the polymer solid electrolyte; the solid electrolyte of the polyfluorinated group polymer has high ionic conductivity and high lithium ion migration number at room temperature and high mechanical strength, and avoids potential safety hazards caused by decomposition of the liquid electrolyte because the liquid electrolyte is avoided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the solid electrolyte material of the polyfluorinated polymer is characterized by comprising 25-30 parts by weight of plasticizer, 60-65 parts by weight of polymer matrix and 10-15 parts by weight of lithium salt; the polymer matrix is a polyfluorinated group polymer formed by polymerizing methyl methacrylate and dodecafluoroheptyl acrylate monomers.
Further, the molecular structure of the polyfluorinated polymer matrix is as follows:
wherein n and m represent the number of moles of the repeating unit, and n: m is 1 (1-2).
Still further, the polyfluoroyl polymer may have a molecular weight (Mw) in the range of 50,000 to 1,000,000, specifically 100,000 to 300,000.
Further, the plasticizer is succinonitrile plastic crystal, and the addition amount of the succinonitrile is 1/4-1/2 of that of the polyfluorinated group polymer.
Further, the lithium salt is two types of lithium bistrifluoromethane sulfonyl imide and lithium difluorooxalate borate, wherein the mass ratio of the lithium difluorooxalate borate to the lithium bistrifluoromethane sulfonyl imide is 1 (1-10), and the addition mass of the lithium salt is 1/10-1/7 of that of the polyfluorinated group polymer.
Further, the preparation method of the polyfluorinated group polymer comprises the following steps:
step 1, according to the mole ratio of 1:1, accurately weighing methyl methacrylate and dodecafluoroheptyl acrylate solution, and dissolving the solution in butyl acetate, wherein the dissolving process is as follows: continuously stirring at 60-90 ℃ for 1-5h to obtain uniform transparent solution;
step 2, ammonium persulfate is selected as an initiator of polymerization reaction, and the mass of the ammonium persulfate is 0.1-0.5% of that of the dodecafluoroheptyl acrylate; the octadecyl mercaptan is selected as a chain extension modifier, and the addition mass of the octadecyl mercaptan is still 0.1-0.5% of the mass of the dodecafluoroheptyl acrylate; placing an initiator and a chain extension modifier into the uniform transparent solution prepared in the step 1;
step 3, placing the mixture solution obtained in the step 2 into a closed container for sealing, and continuously reacting for 3-6 hours at 60-90 ℃ to obtain viscous fluid;
and 4, precipitating and purifying the product obtained in the step 3 for multiple times to obtain a polyfluorinated group polymer product.
Further, the preparation method of the polyfluorinated polymer solid electrolyte material comprises the following steps:
step 1, placing lithium salt in a glove box in an argon atmosphere, and heating at 50-80 ℃ for 1-5h to sufficiently remove water;
step 2, dissolving lithium salt, plasticizer and polymer matrix in acetonitrile/N-methyl pyrrolidone mixed solvent to obtain mixed solution;
step 3, magnetically stirring the mixed solution obtained in the step 2 at 50-80 ℃ for 1-5 hours to obtain uniform electrolyte slurry;
and step 4, immersing the dried glass fiber porous membrane into the electrolyte slurry obtained in the step 3 for 5-10 min, taking out and drying in a drying oven to obtain the polyfluorinated polymer solid electrolyte material.
Further, in the step 2, the volume ratio of acetonitrile to N-methylpyrrolidone in the acetonitrile/N-methylpyrrolidone mixed solvent is 1:1, the solvent accounts for 1/5 of the mass of the mixed solution (lithium salt + plasticizer + polymer matrix + solvent).
The working principle of the invention is as follows:
the polymer is formed by copolymerizing a reactive dodecafluoroheptyl methacrylate monomer and an inert methyl methacrylate monomer, and is shown as follows:
wherein the methyl methacrylate repeating unit ensures the mechanical strength of the polymer so that the electrolyte membrane has sufficient strength to inhibit the continuous growth of lithium dendrites during charge and discharge; the fluorocarbon group in the dodecafluoroheptyl acrylate can be used as a Lewis alkaline site to adsorb Lewis acidic lithium ions, so that a channel is provided for migration of the lithium ions; the flexible side chain plays a solvation and desolvation role, is beneficial to negative charge delocalization in the electrolyte, so that the electrolyte has enough carrier concentration and high lithium ion migration number; f and O atoms on the side chain have strong electron-withdrawing effect, and are favorable for dissolving and dissociating lithium salt. The plasticizer succinonitrile has a large dielectric constant and plays a role of a lubricant in reducing the internal friction among polymer molecules; the succinonitrile plasticizer can also change the morphological structure of the polymer through interaction with polar groups on the molecular chain of the polymer, inhibit crystallization and improve the movement capability of chain segments. Lithium salt selected from lithium bis (trifluoromethanesulfonyl) imide (TFSI) - ) And lithium difluorooxalato borate (DFOB) - ) Two kinds of lithium salt with certain concentration ensure succinonitrile and TFSI - /DFOB - The stronger hydrogen bond action and coordination action between succinonitrile and alkali metal ions reduce free succinonitrile molecules in the electrolyte, and inhibit side reactions between the succinonitrile and lithium metal.
In summary, the beneficial effects of the invention are as follows:
1. the invention provides a polyfluorinated polymer matrix, which selects polymer monomers: the polymer with a cross-linked structure is formed by using ammonium persulfate as an initiator, and using octadecyl mercaptan as a chain extension modifier to carry out free radical copolymerization polymerization reaction on two monomers, wherein a polyfluoro group provides a channel for lithium ion diffusion, lithium ions complete migration through adsorption and desorption with the polyfluoro group, and methyl methacrylate repeating units can provide necessary mechanical strength for the polymer.
2. The invention provides a solid electrolyte material of polyfluorinated polymer, which is formed by blending the polyfluorinated polymer matrix, a plasticizer and lithium salt, and the succinonitrile is used as the plasticizer to reduce the crystallinity of the polymer and increase the free volume for lithium ion migration; meanwhile, a certain concentration of lithium salt can provide necessary Li carriers, and can interact with succinonitrile to inhibit side reactions of the succinonitrile and lithium metal. Based on the method, the polymer solid electrolyte has the advantages of high ionic conductivity, high lithium ion migration number, high mechanical strength and the like, and meanwhile, the potential safety hazard caused by the decomposition of the liquid electrolyte is avoided because the liquid electrolyte is avoided. In particular, the polymer solid electrolyte has a molecular weight of up to (2.51-5.85). Times.10 at normal temperature -4 S cm -1 The migration number of lithium ions reaches 0.47, and the electrochemical stability window is 0-4.714V; li|LiFePO assembled by using the polymer solid electrolyte 4 The specific discharge capacity of the all-solid-state battery at the 0.1C rate reaches 163.2mAh/g, the specific discharge capacity of the Li|NCM811 all-solid-state battery at the 0.1C rate reaches 211.7mAh/g, and the specific capacity level exerted by the liquid electrolyte is even exceeded.
3. The invention also provides a preparation method of the polyfluorinated group polymer matrix and the polymer solid electrolyte, wherein the polyfluorinated group polymer matrix is prepared into an active electrolyte main body (polymer matrix) through one-step polymerization reaction of two monomers by adopting a free radical polymerization method, and the preparation method is simple and has high synthesis efficiency; for the polymer solid electrolyte, the polymer matrix with multiple fluorinated groups, the plasticizer and the lithium salt are blended and cast into a glass fiber film to obtain the polymer solid electrolyte, and the method has the advantages of short process flow, short working procedure time, easiness in control, milder reaction conditions and higher production efficiency; the obtained polymer solid electrolyte does not contain any solvent component or combustible component, avoids burning, ensures the safety, meets the characteristics of all-solid batteries and meets the use requirements of all-solid battery solid electrolytes.
Drawings
Fig. 1 is an ac impedance spectrum of a polymer solid electrolyte prepared in example 1 of the present invention at different temperatures.
Fig. 2 is a high temperature conductivity and Arrhenius fit of the polymer solid electrolyte prepared in example 1 of the present invention.
FIG. 3 is a linear voltammogram of a polymer solid electrolyte prepared in example 1 of the present invention.
FIG. 4 is a timing chart (inset) of the polymer solid electrolyte prepared in example 1 of the present invention.
FIG. 5 shows the use of the polymer solid electrolyte according to example 1 of the present invention for LiFePO 4 Charge-discharge curve at Li solid state battery.
Fig. 6 is a charge-discharge curve of the polymer solid electrolyte provided in example 1 of the present invention when used in an NCM811|li solid-state battery.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, comparative examples and drawings, but the embodiments of the present invention are not limited thereto.
The glass fiber membrane used in the polymer solid electrolyte used in the examples below was identified as GF/C and had a pore size of 1.2 μm and was produced by Whatman, UK.
The ion conductivity test in the following examples adopts an alternating current impedance method, and is measured by using an electrochemical workstation of Shanghai Chenhua CHI660e, and the frequency response range is 1 Hz-1 MHz; during testing, firstly, preparing a stainless steel sheet/polymer solid electrolyte membrane/stainless steel sheet blocking electrode, carrying out alternating current impedance test on an electrochemical workstation, measuring the body resistance (impedance) R of the polymer solid electrolyte membrane, and then calculating the conductivity sigma according to the following formula:
where σ, L, R, S are the conductivity, thickness, bulk resistance and area of the polymer solid electrolyte membrane, respectively.
The charge and discharge capacities in the following examples were tested using the marchand blue electrical testThe test system adopts constant current charge-discharge method, expressed as multiplying power C, wherein for LiFePO 4 An all-solid-state battery of the positive electrode, wherein 1 C=170 mA/g, and the charge-discharge voltage interval is 2.5-3.8V; for an all-solid-state battery employing the positive electrode of NCM811, 1c=200 mA/g, the charge-discharge voltage interval is 2.7 to 4.3V.
Example 1
This example provides a Li|LiFePO based on a polyfluorinated group-containing polymer solid electrolyte 4 The all-solid-state battery is prepared by adopting the following process:
step 1, preparing a polyfluorinated group polymer: accurately weighing 0.035mol (3.5 g) of methyl methacrylate and 0.035mol (14 g) of dodecafluoroheptyl methacrylate, dissolving in butyl acetate, placing in a closed container, stirring for 1h at 90 ℃, adding 0.05g of ammonium persulfate as an initiator and 0.05g of octadecyl mercaptan as a chain extender, continuing to react for 3h at 90 ℃, and obtaining viscous polymer fluid after repeated precipitation and purification;
step 2, preparing polymer solid electrolyte slurry: 3g of viscous polymer fluid, 1g of ethanedinitrile, 0.762g of lithium bistrifluoromethane-sulfonyl imide (LTFSI) and 0.07g of lithium difluorooxalato-borate (LDFOB) are dissolved in a mixed solvent consisting of 1mL of acetonitrile and 1mL of N-methylpyrrolidone, and magnetically stirred at 50 ℃ for 5 hours to obtain a uniform electrolyte slurry;
step 3, preparing a polymer solid electrolyte membrane: cutting a glass fiber porous membrane with the diameter of 19 mm and the thickness of 85 micrometers, soaking in electrolyte slurry for 8 minutes, taking out, and removing acetonitrile and N-methylpyrrolidone solvent in a drying oven to obtain a solid electrolyte membrane;
step 4. Preparation of Li|LiFePO 4 All-solid-state battery: before CR2025 shell encapsulation, a small amount of electrolyte slurry is dripped on two sides of an electrolyte membrane, and is stacked in a button cell positive electrode shell according to the sequence of lithium metal sheets, electrolyte membrane and positive electrode sheets from top to bottom, the positive electrode shell is dried for more than 8 hours at 60 ℃ to fully remove acetonitrile and N-methyl pyrrolidone solvent, and then the cell is encapsulated in a sealing way.
The electrolyte membrane prepared by the process is at different temperaturesThe AC impedance spectrum is shown in FIG. 1, and the effective area of the blocking electrode is 2.0096cm 2 The ion conductivities of the electrolyte membranes obtained at different temperatures, with a thickness of 85 μm for the glass fiber film thickness, are shown in table 1:
TABLE 1 conductivity values of polymer solid electrolytes
According to fig. 2, the electrolyte activation energy was 0.055eV, as obtained from different temperature conductivities and Arrhenius fits.
The linear voltammogram of the resulting electrolyte membrane is shown in fig. 3, and the electrolyte has a decomposition potential of approximately 4.713V.
The li|stainless steel sheet battery was assembled to perform a chronoamperometry and impedance tests before and after polarization, respectively, to calculate the effective carrier ratio in the electrolyte, i.e., the lithium ion migration number, as shown in fig. 4, to obtain a lithium ion migration number of 0.47.
For Li|LiFePO 4 The all-solid-state battery was subjected to charge and discharge test at a current density of 0.1C and a temperature of 25℃, as shown in fig. 5, and the data showed that the solid-state battery was less polarized and exhibited a higher initial discharge specific capacity, reaching 163.2mAh g -1 。
Example 2
This example was prepared by the same method as in example 1, except that a polymer solid electrolyte membrane was assembled in a li|ncm811 all-solid-state battery.
As shown in FIG. 6, the polymer solid electrolyte prepared in this example shows a charge-discharge curve in a Li|NCM811 all-solid-state battery, and the Li|NCM811 all-solid-state battery shows 211.7mAh g at a current density of 0.1C and 25 ℃ -1 Is a specific capacity of the first discharge.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (3)
1. The solid electrolyte material of the polyfluorinated polymer is characterized by being formed by blending 25-30 parts by weight of a plasticizer, 60-65 parts by weight of a polymer matrix and 10-15 parts by weight of lithium salt; the polymer matrix is a polyfluorinated polymer formed by polymerizing methyl methacrylate and dodecafluoroheptyl acrylate monomers;
the molecular structure of the polyfluorinated polymer matrix is as follows:
wherein n and m represent the number of moles of the repeating unit, and n: m is 1 (1-2);
the molecular weight of the polyfluorinated group polymer is 100,000-300,000, and the plasticizer is succinonitrile plastic crystal; the lithium salt is two types of lithium bis (trifluoromethanesulfonyl) imide and lithium difluoro (oxalato) borate, wherein the mass ratio of the lithium difluoro (oxalato) borate to the lithium bis (trifluoromethanesulfonyl) imide is 1 (1-10);
the polyfluorinated group polymer is prepared by the steps of:
step 1, accurately weighing methyl methacrylate and dodecafluoroheptyl acrylate solution according to a molar ratio of 1:1, and dissolving the solution in butyl acetate, wherein the dissolving process is as follows: continuously stirring at 60-90 ℃ for 1-5h to obtain uniform transparent solution;
step 2, ammonium persulfate is selected as an initiator of polymerization reaction, and the mass of the ammonium persulfate is 0.1-0.5% of that of the dodecafluoroheptyl acrylate; octadecyl mercaptan is selected as a chain extension modifier, and the added mass of the octadecyl mercaptan is 0.1-0.5% of the mass of the dodecafluoroheptyl acrylate; placing an initiator and a chain extension modifier into the uniform transparent solution prepared in the step 1;
step 3, placing the mixture solution obtained in the step 2 into a closed container for sealing, and continuously reacting for 3-6 hours at 60-90 ℃ to obtain viscous fluid;
and 4, precipitating and purifying the product obtained in the step 3 for multiple times to obtain a polyfluorinated group polymer product.
2. The polyfluorinated polymer solid electrolyte material according to claim 1, wherein said polyfluorinated polymer solid electrolyte material is prepared by a process comprising the steps of:
step 1, placing lithium salt in a glove box in argon atmosphere, and heating for 1-5h at 50-80 ℃;
step 2, dissolving lithium salt, plasticizer and polymer matrix in acetonitrile/N-methyl pyrrolidone mixed solvent to obtain mixed solution;
step 3, magnetically stirring the mixed solution obtained in the step 2 at 50-80 ℃ for 1-5 hours to obtain uniform electrolyte slurry;
and step 4, immersing the dried glass fiber porous membrane into the electrolyte slurry obtained in the step 3 for 5-10 min, taking out and drying in a drying oven to obtain the polyfluorinated polymer solid electrolyte material.
3. The solid electrolyte material of polyfluorinated polymer according to claim 2, wherein in the step 2, the volume ratio of acetonitrile to N-methylpyrrolidone in the acetonitrile/N-methylpyrrolidone mixed solvent is 1:1, and the solvent accounts for 1/5 of the mass of the mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110946301.3A CN113707935B (en) | 2021-08-18 | 2021-08-18 | Polyfluorinated polymer solid electrolyte material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110946301.3A CN113707935B (en) | 2021-08-18 | 2021-08-18 | Polyfluorinated polymer solid electrolyte material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113707935A CN113707935A (en) | 2021-11-26 |
| CN113707935B true CN113707935B (en) | 2023-08-08 |
Family
ID=78653270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110946301.3A Active CN113707935B (en) | 2021-08-18 | 2021-08-18 | Polyfluorinated polymer solid electrolyte material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113707935B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020143259A1 (en) * | 2019-01-10 | 2020-07-16 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3615391B2 (en) * | 1998-05-08 | 2005-02-02 | 株式会社リコー | Ion conductive polymer solid electrolyte and battery using the solid electrolyte |
| KR100413800B1 (en) * | 2001-10-17 | 2004-01-03 | 삼성에스디아이 주식회사 | Fluoride copolymer, polymer electrolyte comprising the same and lithium battery employing the polymer electrolyte |
| KR101925931B1 (en) * | 2012-12-10 | 2018-12-06 | 삼성에스디아이 주식회사 | Block copolymers for lithium polymer batteries, electrolytes containing the same and lithium polymer batteries |
| US10084220B2 (en) * | 2016-12-12 | 2018-09-25 | Nanotek Instruments, Inc. | Hybrid solid state electrolyte for lithium secondary battery |
| CN109326822B (en) * | 2018-11-05 | 2020-11-17 | 珠海冠宇电池股份有限公司 | Preparation method of all-solid fluoropolymer electrolyte membrane and lithium ion battery |
-
2021
- 2021-08-18 CN CN202110946301.3A patent/CN113707935B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020143259A1 (en) * | 2019-01-10 | 2020-07-16 | 北京工业大学 | Preparation and application of polycarbonate-based polymer electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| Electrical Properties of Lithium-Ion Conducting Poly (Vinylidene Fluoride-Co-Hexafluoropropylene) (PVDF-HFP)/Polyvinylpyrrolidone (PVP) Solid Polymer Electrolyte;Karpagavel, K. 等;Journal of Electronic Materials;第50卷;4415–4425 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113707935A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608592B (en) | Cross-linking polymerization preparation method of polyion liquid solid electrolyte | |
| CN103509153B (en) | A kind of polymer list ionic electrolytes and preparation method thereof | |
| CN109950614B (en) | Polymer solid electrolyte preparation method, polymer solid electrolyte secondary lithium battery and preparation method | |
| CN108923064B (en) | Solid polymer electrolyte, preparation method thereof and lithium ion secondary battery | |
| CN111554974A (en) | Preparation method of polyethylene glycol diacrylate-based gel electrolyte | |
| CN109585919B (en) | Lithium ion battery and electrolyte thereof | |
| CN110828891B (en) | Sulfur-containing polymer solid electrolyte and preparation method and application thereof | |
| CN111647345B (en) | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof | |
| CN114039097A (en) | Lithium ion battery | |
| CN112993395A (en) | Lithium single-ion polyimide gel polymer electrolyte, different plasticizers and preparation process | |
| CN113707935B (en) | Polyfluorinated polymer solid electrolyte material and preparation method thereof | |
| CN114464880B (en) | Self-repairing composite solid lithium ion battery electrolyte and preparation method thereof | |
| CN113571768B (en) | Modified aluminum-based polymer and preparation method thereof, high-pressure-resistant solid polymer electrolyte membrane and preparation method thereof, and lithium metal secondary battery | |
| CN111987351B (en) | Polymer gel electrolyte and preparation method and application thereof | |
| CN115149097A (en) | Preparation method of gel polymer electrolyte and secondary lithium battery | |
| CN115716896A (en) | Polyethylene oxide comb polymer and preparation method and application thereof | |
| CN111748061A (en) | Solid polymer electrolyte, preparation method thereof and lithium ion battery | |
| CN113540559B (en) | ZIF-8@ PEGMEM-co-AMPS-Li single ion polymer solid electrolyte and preparation method thereof | |
| CN117457978B (en) | Amphoteric gel electrolyte for solid lithium ion battery and preparation method thereof | |
| CN115745798B (en) | Polydioxolane three-dimensional crosslinked polymer electrolyte and preparation method and application thereof | |
| CN116231066B (en) | Self-repairing gel polymer electrolyte and preparation method thereof | |
| CN116231068B (en) | Solid electrolyte membrane, preparation method thereof and solid lithium metal battery | |
| CN117374380A (en) | Single-ion conductor polymer electrolyte and preparation method and application thereof | |
| CN117239227A (en) | In-situ polymerization all-solid-state polymer electrolyte and preparation method and application thereof | |
| WO2020119750A1 (en) | Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte solution, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |