CN112397780A - Polymer electrolyte film material and preparation method thereof - Google Patents
Polymer electrolyte film material and preparation method thereof Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 72
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 72
- 239000010455 vermiculite Substances 0.000 claims abstract description 58
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 58
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 54
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000012047 saturated solution Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229920006254 polymer film Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 238000005266 casting Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 25
- 239000003792 electrolyte Substances 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
-
- 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
Abstract
The invention discloses a polymer electrolyte film material and a preparation method thereof. Stripping vermiculite by adopting sodium chloride and lithium chloride saturated solution to prepare two-dimensional lamellar vermiculite; then, carrying out acid etching on the two-dimensional lamellar vermiculite by adopting a hydrochloric acid solution to obtain porous two-dimensional nano vermiculite lamellar, namely VNs; doping a PEO/PVDF-HFP blended polymer by using VNs as a filler to obtain a PEO/PVDF-HFP/VNs polymer film, wherein the PEO is polyethylene oxide, and the PVDF-HFP is polyvinylidene fluoride-hexafluoropropylene; and then soaking the PEO/PVDF-HFP/VNs polymer film by adopting organic electrolyte to obtain the PEO/PVDF-HFP/VNs polymer electrolyte film material. The polymer electrolyte membrane material prepared by the invention has high ionic conductivity and lithium ion transference number and small interface impedance, effectively improves the electrochemical performance of the lithium battery based on the polymer electrolyte membrane, and the method for preparing the polymer electrolyte membrane has the beneficial effects of simple and easy operation, low cost and easy large-scale preparation.
Description
Technical Field
The invention relates to a polymer electrolyte film, in particular to a polymer electrolyte film material and a preparation method thereof.
Background
With the exhaustion of resources and the increasing severity of environmental issues, energy storage devices have attracted the attention of many researchers. In the battery field, scientists are continuously exploring the research of lead-acid batteries, zinc-manganese batteries, nickel-cadmium batteries, fuel batteries and lithium ion batteries and applying the research in a plurality of fields. Among them, the lithium ion battery has many advantages, such as high specific energy, high battery voltage, less self-discharge, long service life, environmental friendliness, etc., and is widely used in the application fields of electronic products, electric tools, aerospace power sources, large-scale energy storage, etc., due to its attention of many researchers. The conventional lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the electrolyte and the diaphragm are one of main factors determining the safety of the battery, one of the main problems of the commercial lithium ion battery adopting the organic liquid electrolyte and the Celgard film is that the electrolyte is easy to leak and burn to bring a series of potential safety hazards, and the adoption of the solid electrolyte to replace a liquid organic electrolyte-diaphragm system is an effective measure for solving the problems, so that the development of the solid electrolyte with high performance is urgent.
The polymer electrolyte is considered as a solid electrolyte with great application potential because of good flexibility and good compatibility with lithium metal, and the polymer electrolyte is mainly divided into an all-Solid Polymer Electrolyte (SPE) and a Gel Polymer Electrolyte (GPE). In recent years, a great deal of research has been conducted on several gel polymer electrolytes with potential applications. However, GPE mainly faces the problems of low room temperature ionic conductivity, large interface resistance, low electrochemical stable voltage window and the like.
The invention attempts to improve the electrochemical performance of the polymer electrolyte film material by adopting a filler doping mode, successfully solves the problems of low ionic conductivity and large interface impedance of the polymer gel electrolyte at room temperature, and develops the polymer electrolyte film material and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a polymer electrolyte film material and a preparation method thereof. The polymer electrolyte membrane material prepared by the invention has high ionic conductivity and small interface impedance, improves the electrochemical performance of the polymer electrolyte material, and has the characteristics of simple and easy operation, low cost and easy large-scale preparation.
The technical scheme of the invention is as follows: a polymer electrolyte film material is prepared by adopting sodium chloride and lithium chloride saturated solution to strip vermiculite to prepare two-dimensional lamellar vermiculite; then, carrying out acid etching on the two-dimensional lamellar vermiculite by adopting a hydrochloric acid solution to obtain porous two-dimensional nano vermiculite lamellar, namely VNs; doping a PEO/PVDF-HFP blended polymer by using VNs as a filler to obtain a PEO/PVDF-HFP/VNs polymer film, wherein the PEO is polyethylene oxide, and the PVDF-HFP is polyvinylidene fluoride-hexafluoropropylene; and then soaking the PEO/PVDF-HFP/VNs polymer film by adopting an organic electrolyte to obtain the PEO/PVDF-HFP/VNs polymer electrolyte film material.
The preparation method of the polymer electrolyte film material comprises the following steps:
(1) Firstly heating and stripping 8-12g of vermiculite in 100mL of sodium chloride saturated solution at 75-85 ℃ for 22-26h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping the sample for 22-26h at 75-85 ℃ to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding the product A into hydrochloric acid solution, heating and stirring, then stirring and cleaning to be neutral, and drying to obtain a porous two-dimensional nano vermiculite sheet layer, namely VNs, which is a product B;
(3) Adding the product B into the organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring uniformly at 20-30 ℃, pouring into a polytetrafluoroethylene mold, and drying to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C;
(4) And cutting the product C, immersing the product C in organic electrolyte for 10-14h to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
In the preparation method of the polymer electrolyte membrane material, in the step (1), 10g of vermiculite is firstly heated and stripped for 24 hours at 80 ℃ in 100mL of sodium chloride saturated solution to obtain a sample; and dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping at 80 ℃ for 24 hours to obtain the two-dimensional lamellar vermiculite serving as a product A.
In the preparation method of the polymer electrolyte membrane material, in the step (2), 10-20g of the product A is added into 12-36% hydrochloric acid solution according to the following proportion, the solution is heated and magnetically stirred at 70-90 ℃ for 20-40min, then the solution is stirred and cleaned to be neutral, and the solution is dried at 50-70 ℃ for 12-48h to obtain a porous two-dimensional nano vermiculite sheet layer, namely VNs, which is the product B.
In the preparation method of the polymer electrolyte thin film material, in the step (3), the mass ratio of the B product to the PVDF-HFP to the PEO in the C product is 1-2:5:5.
in the preparation method of the polymer electrolyte membrane material, in the step (3), the product B is added into N, N-dimethylformamide or acetonitrile organic solution to be stirred and dispersed, then PVDF-HFP and PEO polymer are sequentially added, stirring is continuously carried out for 6-10 hours at 20-30 ℃, then the mixture is poured into a polytetrafluoroethylene mold and dried for 10-12 hours at 50-70 ℃, and the PEO/PVDF-HFP/VNs polymer membrane, namely the product C, is obtained.
In the preparation method of the polymer electrolyte membrane material, in the step (4), the organic electrolyte is 1M LiPF-containing electrolyte 6 The EC/EMC/DEC solution of (1), wherein the volume ratio of EC, EMC and DEC is 1.
In the polymer electrolyte membrane material, a PEO/PVDF-HFP/VNs polymer electrolyte membrane material is adopted to prepare the lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the patent adopts two polymers of PEO and PVDF-HFP as matrixes to blend to prepare polymer gel electrolyte (GPE). In order to further improve the electrochemical performance of GPE, organic/inorganic nanofillers are added to GPE.
The Vermiculite (Vermiculite) clay is a natural aluminum silicate layered material, has ionic conductivity and electronic insulation properties, and can be represented as (Mg, ca) in chemical formula 0.7 (Mg，Fe，Al) 6.0 [(Al，Si) 8.0 ](OH 4.8 H2O)。
The method comprises the steps of stripping vermiculite by adopting sodium chloride and lithium chloride saturated solution to prepare two-dimensional lamellar vermiculite; then, carrying out acid etching on the two-dimensional lamellar vermiculite by adopting a hydrochloric acid solution to obtain porous two-dimensional nano vermiculite lamellar, namely VNs; the PEO/PVDF-HFP blended polymer is doped by VNs serving as a filler to obtain a PEO/PVDF-HFP/VNs polymer film, so that the thermal stability of the polymer film can be improved, and a fast path is provided for the transmission of lithium ions because VNs have weak electronegativity.
The PVDF-HFP and PEO are adopted to realize the mutual synergistic effect, the mechanical property and the flexibility are high, the VNs is introduced, the interface compatibility of the polymer and lithium metal is improved, a rapid transmission channel is provided for lithium ions, the chemical stability, the ionic conductivity and the lithium ion migration number of the polymer electrolyte film are improved, and the interface impedance of the electrolyte and an electrode is reduced.
2. The method adopts the organic solvent to disperse and dissolve VNs, PVDF-HFP and PEO polymers, so that the VNs, PVDF-HFP and PEO polymers are fully and uniformly mixed in the process of magnetic stirring, and a film is directly formed by using a solution pouring method. The preparation method is simple and environment-friendly, and has great application potential in energy storage devices such as batteries and the like. Specifically, the method comprises the steps of firstly preparing two-dimensional lamellar vermiculite by an ion exchange method, then treating the obtained two-dimensional lamellar vermiculite by using acid to prepare a porous two-dimensional nano vermiculite lamellar, then uniformly blending the prepared porous two-dimensional nano vermiculite lamellar with a polymer, preparing a film by a solution pouring method, and finally soaking the film in electrolyte to obtain the polymer electrolyte film material.
3. Vermiculite is widely used for preparing heat insulation building materials as an abundant natural two-dimensional clay material, and the two-dimensional nano vermiculite obtained after modification has wider application prospect, but has a plurality of difficulties for preparing the two-dimensional nano vermiculite by using the natural vermiculite. Firstly, the presence of a large amount of impurities in natural vermiculite is not easily removed, which reduces the purity of the two-dimensional nanomaterial, and secondly, for vermiculite materials of 1. Based on the problem, firstly, sodium ions with large atomic radius enter the space between the sheets to strip the sheet structure, and then, lithium ions with strong hydration capability are used for further ion exchange, so that the stripping effect is achieved. The thickness of the obtained two-dimensional lamellar vermiculite is about 3nm, which is a typical two-lamellar structure of 1.
Experiments prove that:
the PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared by the method has excellent electrochemical performance.
Applicants constructed lithium button cells based on the PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared according to the examples and tested the devices for performance. Table 1 is a comparison of electrochemical properties of the PEO/PVDF-HFP/VNs polymer electrolyte membrane material of the present invention and other related polymer electrolyte membrane materials, and the results show that the electrochemical properties of the PEO/PVDF-HFP/VNs polymer electrolyte membrane material obtained by the present invention are at a higher level, as detailed in table 1;
TABLE 1 comparison of electrochemical Properties of Polymer electrolyte Membrane Material of the present invention and existing Polymer electrolyte Membrane Material
FIG. 1 is a graph of a PEO/PVDF-HFP/VNs polymer film prepared by the present invention after cutting; from FIG. 1, it can be seen that the PEO/PVDF-HFP/VNs polymer film obtained by the present invention has good flexibility;
FIG. 2 is a graph of the resistance of a PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared according to the present invention, wherein the ionic conductivity of the polymer electrolyte membrane material meets the performance requirements of a lithium ion battery; from FIG. 2, it can be calculated that the ionic conductivity of the PEO/PVDF-HFP/VNs polymer electrolyte thin-film material is 2.8X 10 -3 S/cm；
FIG. 3 is a graph showing the interfacial resistance between the PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared by the present invention and the lithium metal cathode, and it can be seen from FIG. 3 that the PEO/PVDF-HFP/VNs polymer electrolyte membrane material has an interfacial resistance of only 50 Ω;
fig. 4 is an atomic force scanning electron microscope image of a porous two-dimensional nano vermiculite lamella obtained by acid treatment modification, and it can be seen from fig. 4 that obvious pores exist on the surface of the two-dimensional lamella, and rich pore structures and cation vacancies further provide a channel for rapid lithium ion transmission, which is beneficial to improvement of the ionic conductivity and the transference number of lithium ions of the PEO/PVDF-HFP/VNs electrolyte.
In conclusion, the polymer electrolyte membrane material prepared by the invention has the advantages of high ionic conductivity and lithium ion transference number and small interfacial impedance, effectively improves the comprehensive electrochemical performance of the lithium battery based on the polymer electrolyte membrane material, and has the beneficial effects of simple and easy operation, low cost and easy large-scale preparation.
Drawings
FIG. 1 is a schematic representation of a PEO/PVDF-HFP/VNs polymer film produced by the present invention after cutting;
FIG. 2 is a graph of the electrical resistance of a PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared in accordance with the present invention;
FIG. 3 is a graph of the interfacial resistance of the PEO/PVDF-HFP/VNs polymer electrolyte membrane material prepared by the present invention to a lithium metal negative electrode;
fig. 4 is an atomic force micrograph of porous two-dimensional nano-vermiculite sheets obtained by acid treatment modification.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Embodiment 1, a method for preparing a polymer electrolyte membrane material, comprising the steps of:
(1) Firstly heating 8g of vermiculite in 100mL of sodium chloride saturated solution at 75 ℃ and stripping for 22h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping for 22h at 75 ℃ to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding 10g of product A into 12% hydrochloric acid solution, heating at 70 deg.C, magnetically stirring for 20min, stirring, cleaning to neutrality, and drying at 50 deg.C for 12h to obtain porous two-dimensional nano-vermiculite sheet layer (VNs) as product B.
(3) Adding the product B into an N, N-dimethylformamide or acetonitrile organic solution, stirring and dispersing, sequentially adding PVDF-HFP and a PEO polymer, continuously stirring for 6 hours at 20 ℃, pouring into a polytetrafluoroethylene mold, and drying for 10 hours at 50 ℃ to obtain a PEO/PVDF-HFP/VNs polymer film serving as a product C; and the mass ratio of the product B to the PVDF-HFP to the PEO in the product C is 1:5:5;
(4) Cutting product C into film, soaking in organic electrolyte (containing 1M LiPF) 6 The (1) is soaked for 10 hours in the EC/EMC/DEC (1, v/v)), so as to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
(1) Firstly, heating and stripping 10g of vermiculite in 100mL of sodium chloride saturated solution at 80 ℃ for 24 hours to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping the sample at 80 ℃ for 24h to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding 15g of product A into 20% hydrochloric acid solution, heating at 80 deg.C, magnetically stirring for 30min, stirring, cleaning to neutrality, and drying at 60 deg.C for 20h to obtain porous two-dimensional nano vermiculite sheet layer (VNs) as product B.
(3) Adding the product B into N, N-dimethylformamide or acetonitrile organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring at 25 ℃ for 7h, pouring into a polytetrafluoroethylene mold, and drying at 60 ℃ for 11h to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C; the mass ratio of the B product, PVDF-HFP and PEO in the C product is 1.5:5:5;
(4) Cutting product C into film, soaking in organic electrolyte (containing 1M LiPF) 6 The electrolyte membrane is soaked in the EC/EMC/DEC (1, v/v)) for 12 hours to obtain a PEO/PVDF-HFP/VNs polymer electrolyte membrane material, namely a finished product.
Embodiment 3, a method for preparing a polymer electrolyte membrane material, comprising the steps of:
(1) Firstly, heating and stripping 10g of vermiculite in 100mL of sodium chloride saturated solution at 80 ℃ for 26h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping the sample at 80 ℃ for 24h to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding 18g of product A into 30% hydrochloric acid solution, heating at 90 deg.C, magnetically stirring for 30min, stirring, cleaning to neutrality, and drying at 60 deg.C for 36h to obtain porous two-dimensional nano-vermiculite sheet layer (VNs) as product B.
(3) Adding the product B into N, N-dimethylformamide or acetonitrile organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring at 20 ℃ for 10h, pouring into a polytetrafluoroethylene mold, and drying at 60 ℃ for 11h to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C; the mass ratio of B product, PVDF-HFP and PEO in the C product is 1.8:5:5;
(4) Cutting product C into film, soaking in organic electrolyte (containing 1M LiPF) 6 The (1) is soaked for 13h in the EC/EMC/DEC (1, v/v)), so as to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
(1) Firstly, heating and stripping 10g of vermiculite in 100mL of sodium chloride saturated solution at 85 ℃ for 22h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping at 80 ℃ for 24 hours to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding product 13gA into 256% hydrochloric acid solution, heating at 90 deg.C, magnetically stirring for 40min, stirring, cleaning to neutrality, and drying at 50 deg.C for 40h to obtain porous two-dimensional nano vermiculite sheet layer (VNs) as product B.
(3) Adding the product B into N, N-dimethylformamide or acetonitrile organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring for 8h at 28 ℃, pouring into a polytetrafluoroethylene mold, and drying for 12h at 55 ℃ to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C; and the mass ratio of the B product to the PVDF-HFP to the PEO in the C product is 1.7:5:5;
(4) Cutting product C into film, soaking in organic electrolyte (containing 1M LiPF) 6 The (1) is soaked for 10 hours in the EC/EMC/DEC (1, v/v)), so as to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
(1) Firstly, heating and stripping 12g of vermiculite in 100mL of sodium chloride saturated solution at 85 ℃ for 26h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping the sample for 26 hours at 85 ℃ to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding 20g of product A into 36% hydrochloric acid solution, heating at 90 deg.C, magnetically stirring for 40min, stirring, cleaning to neutrality, and drying at 70 deg.C for 48h to obtain porous two-dimensional nano-vermiculite sheet layer (VNs) as product B.
(3) Adding the product B into N, N-dimethylformamide or acetonitrile organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring at 30 ℃ for 10h, pouring into a polytetrafluoroethylene mold, and drying at 70 ℃ for 12h to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C; and the mass ratio of the product B to the PVDF-HFP to the PEO in the product C is 2:5:5;
(4) Cutting product C into film, soaking in organic electrolyte (containing 1M LiPF) 6 The (1) is soaked for 14 hours in the EC/EMC/DEC (1, v/v)), so as to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
Claims (8)
1. A polymer electrolyte membrane material characterized by: stripping vermiculite by adopting sodium chloride and lithium chloride saturated solution to prepare two-dimensional lamellar vermiculite; then, carrying out acid etching on the two-dimensional sheet layer vermiculite by adopting a hydrochloric acid solution to obtain a porous two-dimensional nano vermiculite sheet layer, namely VNs; doping a PEO/PVDF-HFP blended polymer by using VNs as a filler to obtain a PEO/PVDF-HFP/VNs polymer film, wherein the PEO is polyethylene oxide, and the PVDF-HFP is polyvinylidene fluoride-hexafluoropropylene; and then soaking the PEO/PVDF-HFP/VNs polymer film by adopting an organic electrolyte to obtain the PEO/PVDF-HFP/VNs polymer electrolyte film material.
2. The method for preparing a polymer electrolyte membrane material according to claim 1, characterized in that: the method comprises the following steps:
(1) Firstly heating and stripping 8-12g of vermiculite in 100mL of sodium chloride saturated solution at 75-85 ℃ for 22-26h to obtain a sample; dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping at 75-85 ℃ for 22-26h to obtain two-dimensional lamellar vermiculite serving as a product A;
(2) Adding the product A into hydrochloric acid solution, heating and stirring, then stirring and cleaning to be neutral, and drying to obtain a porous two-dimensional nano vermiculite sheet layer, namely VNs, which is a product B;
(3) Adding the product B into the organic solution, stirring and dispersing, sequentially adding PVDF-HFP and PEO polymer, continuously stirring uniformly at 20-30 ℃, pouring into a polytetrafluoroethylene mold, and drying to obtain a PEO/PVDF-HFP/VNs polymer film which is a product C;
(4) And cutting the product C into a film, immersing the film in an organic electrolyte for 10-14h to obtain a PEO/PVDF-HFP/VNs polymer electrolyte film material, namely a finished product.
3. The method for producing a polymer electrolyte membrane material according to claim 2, characterized in that: in the step (1), firstly, 10g of vermiculite is heated and stripped for 24 hours at 80 ℃ in 100mL of sodium chloride saturated solution to obtain a sample; and dispersing the sample in 100mL of lithium chloride saturated solution, and heating and stripping at 80 ℃ for 24 hours to obtain the two-dimensional lamellar vermiculite serving as a product A.
4. The method for producing a polymer electrolyte membrane material according to claim 2, characterized in that: in the step (2), 10-20g of product A is added into 12-36% hydrochloric acid solution according to the following proportion, the solution is heated and magnetically stirred for 20-40min at 70-90 ℃, then the solution is stirred and cleaned to be neutral, and the solution is dried for 12-48h at 50-70 ℃, so that porous two-dimensional nano vermiculite sheets, namely VNs, are obtained and are product B.
5. The method for producing a polymer electrolyte membrane material according to claim 2, characterized in that: in the step (3), the mass ratio of B product, PVDF-HFP and PEO in C product is 1-2:5:5.
6. the method for producing a polymer electrolyte membrane material according to claim 2, characterized in that: in the step (3), the product B is added into N, N-dimethylformamide or acetonitrile organic solution to be stirred and dispersed, PVDF-HFP and PEO polymer are sequentially added, stirring is continuously carried out for 6-10 hours at 20-30 ℃, then casting is carried out in a polytetrafluoroethylene mold, and drying is carried out for 10-12 hours at 50-70 ℃ to obtain the PEO/PVDF-HFP/VNs polymer film which is the product C.
7. The method for producing a polymer electrolyte membrane material according to claim 2, characterized in that: in the step (4), the organic electrolyte contains 1M LiPF 6 The EC/EMC/DEC solution of (1), wherein EC,The volume ratio of EMC to DEC is 1.
8. The polymer electrolyte membrane material according to claim 1, characterized in that: the PEO/PVDF-HFP/VNs polymer electrolyte membrane material is adopted to prepare the lithium battery.
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