CN113839145B - Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof - Google Patents

Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof Download PDF

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CN113839145B
CN113839145B CN202111095615.3A CN202111095615A CN113839145B CN 113839145 B CN113839145 B CN 113839145B CN 202111095615 A CN202111095615 A CN 202111095615A CN 113839145 B CN113839145 B CN 113839145B
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ionic liquid
hfp
pvdf
hexafluoropropylene
salt
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CN113839145A (en
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谢德龙
卢庆
谢于辉
吴华
梅毅
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Kunming University of Science and Technology
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an electrolyte membrane based on PVDF-HFP and ionic liquid, which is prepared from polyvinylidene fluoride-hexafluoropropylene powder, li salt and ionic liquid according to a specific proportion. According to the invention, the Li salt is mixed with the ionic liquid in the polymer polyvinylidene fluoride-hexafluoropropylene, and the ionic liquid acts as a plasticizer and a charge carrier in the gel, so that the obtained electrolyte membrane has high ionic conductivity, and simultaneously has good thermal stability and safety, and can be used as a membrane of various high-performance safe lithium ion batteries so as to meet the requirements of people on the high-performance safe lithium ion batteries.

Description

Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery electrolyte diaphragms, in particular to an electrolyte diaphragm based on PVDF-HFP and ionic liquid and a preparation method thereof.
Background
In the research of rechargeable batteries, two key issues that are of interest are battery performance and its safety performance. Lithium Metal Batteries (LMBs) are lithium ion batteries that use metallic lithium as the anode, and are considered to be one of the most promising high-performance battery systems. However, since it reacts with organic electrolyte, lithium metal as an anode causes serious problems such as uneven lithium deposition and formation of lithium dendrite during charge and discharge cycles, resulting in short circuit of the battery and potential safety hazard. These problems pose a serious impediment to practical production applications of LMBs. In addition, in practical production applications of lithium ion batteries, the commonly used electrolyte is composed of Li salts dissolved in aprotic molecular solvents, such as diethyl carbonate and ethylene carbonate. Although these carbonate-based electrolytes ensure a high energy density for the battery, their flammable, volatile instability presents further problems for the safety performance of lithium ion batteries.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an electrolyte membrane based on PVDF-HFP and ionic liquid. The Li salt is mixed with an ionic liquid in the polymer, which functions as a plasticizer and charge carrier in the gel, so that the ionic conductivity can be made in a relatively high range. In the application research of different polymers, the polymer prepared by taking polyvinylidene fluoride-hexafluoropropylene as a matrix has the advantages of excellent mechanical property, heat stability and good compatibility with ionic liquid, and meanwhile, the ionic gel electrolyte can inhibit the formation of lithium dendrites in a lithium battery. Therefore, the method can be used for preparing the electrolyte membrane with higher ionic conductivity and good safety, thereby meeting the current market requirements on batteries.
Another object of the invention is to provide a method for preparing an electrolyte membrane based on PVDF-HFP and an ionic liquid.
To achieve the above object, the present invention is achieved by: the electrolyte membrane based on PVDF-HFP and ionic liquid is prepared from the following components in percentage by mass:
20 to 35 percent of polyvinylidene fluoride-hexafluoropropylene powder
60 To 73 percent of ionic liquid
5-7% Of Li salt.
The ionic liquid is one of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-methyl-3-hexylimidazole fluorine-containing methylsulfonylimine salt, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-n-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
The Li salt is lithium bistrifluoromethylsulfonylimide.
The polyvinylidene fluoride-hexafluoropropylene powder is prepared from the following components in percentage by mass:
50 to 60 percent of polyvinylidene fluoride-hexafluoropropylene emulsion
3 To 10 percent of anion-cation exchange resin
30-45% Of electrolyte.
The preparation method comprises the following steps:
(1) Weighing anion-cation exchange resin and polyvinylidene fluoride-hexafluoropropylene emulsion according to the formula proportion, and mixing for 4-6 hours under the stirring action to form mixed emulsion;
(2) Filtering the mixed emulsion to obtain viscous polyvinylidene fluoride-hexafluoropropylene emulsion after adsorption;
(3) Dropwise adding electrolyte into the adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion in a dropwise adding mode while stirring to prepare polyvinylidene fluoride-hexafluoropropylene gel;
(4) Drying polyvinylidene fluoride-hexafluoropropylene gel at 40-50 ℃;
(5) The dried polyvinylidene fluoride-hexafluoropropylene gel is ball-milled by a ball mill, and powder below 60 microns is screened out by a screen.
The solid content of the polyvinylidene fluoride-hexafluoropropylene emulsion (PVDF-HFP emulsion) is 25-50%.
The electrolyte is hydrochloric acid solution with the solution concentration of 0.1 mol/L.
In the step (3), electrolyte is added dropwise in a dropwise manner while stirring, so that the emulsion and the electrolyte are uniformly mixed. Preferably, the stirring speed is 400-800rpm.
In the step (5), the ball milling rotating speed is 300-400rpm, and the time is 8-20h.
The polyvinylidene fluoride-hexafluoropropylene emulsion is prepared by dissolving polyvinylidene fluoride-hexafluoropropylene in N, N-dimethylformamide, wherein the content of the polyvinylidene fluoride-hexafluoropropylene is 25-50%.
The anion-cation exchange resin adopted by the polyvinylidene fluoride-hexafluoropropylene powder can effectively adsorb the ionic surfactant in the PVDF-HFP emulsion on the resin; the porosity can reach 80%, nano-scale pore channels which are uniformly distributed are provided for the circulation of electrons, and the conductivity of the polymer can be greatly improved, so that the cycle efficiency of the battery is effectively improved; the manufacturing process is simple, the material sources are wide and economical, the cycle efficiency of the electrolyte is greatly improved, and in practical application, the requirements of the battery on the electrolyte material are met.
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) Weighing Li salt and ionic liquid according to the formula proportion, and dissolving the Li salt in the ionic liquid to obtain a salt-ionic liquid solution;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion for 30-50 min to obtain a uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 120-130 ℃ for 8-15h;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
In the step (1), the process of dissolving the Li salt in the ionic liquid is carried out in a glove box so as to avoid pollution.
In the step (2), the frequency of ultrasonic treatment is 10-30KHz, and the power is 300-600W.
Preferably, in the step (2), the ultrasonic treatment has a frequency of 20KHz and a power of 450W, and has excellent dispersing effect and activation promoting effect.
In the step (2), the film was dried at 125℃for 12 hours.
The thickness of the film was 50 μm when the co-dispersion was coated.
The drying device is a vacuum drying oven.
According to the technical scheme, the Li salt-ionic liquid solution is injected into gaps of polyvinylidene fluoride-hexafluoropropylene, then the gaps are coated into a film with the thickness of 50 microns by a film coater, and the film is dried in vacuum at 125 ℃ to finally obtain the polyvinylidene fluoride-hexafluoropropylene/ionic liquid ionic gel electrolyte diaphragm with good ionic conductivity. The polymer prepared by taking polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) as a matrix has the advantages of excellent mechanical property and thermal stability, and good compatibility with ionic liquid, and meanwhile, the ionic gel electrolyte can inhibit the formation of lithium dendrites in a lithium battery, so that the cycle stability and ionic conductivity of the electrolyte membrane are greatly improved. In view of good performance and simple manufacturing process, the polyvinylidene fluoride-hexafluoropropylene/ionic liquid ionic gel electrolyte membrane synthesized by the invention can be widely applied to the field of battery electrolyte membranes, and has important economic and social significance for the development of lithium ion battery electrolytes.
Compared with the prior art, the invention has the following outstanding effects:
(1) Due to the non-volatility, high thermal stability and high ionic conductivity of the ionic liquid, the traditional liquid electrolyte is replaced, and the safety problem of the lithium battery is solved;
(2) The Li salt is mixed with the ionic liquid in the polymer, and the ionic liquid acts as a charge carrier and a plasticizer in the gel, so that the ionic conductivity of the electrolyte is relatively high, and is usually 10 -4-10-3Scm-1 at room temperature, thereby effectively improving the cycle efficiency of the battery;
(3) The manufacturing process is simple, the material sources are wide and economical, the cycle life and the cycle efficiency of the electrode are greatly improved, in practical application, the requirement of the battery on the electrolyte diaphragm is met, and the electrode can be widely applied to electric vehicle storage batteries, mobile phone batteries, watch electronics and the like.
Description of the drawings:
FIG. 1 is an SEM image of an electrolyte membrane example 1 of the invention based on PVDF-HFP and an ionic liquid;
FIG. 2 is an SEM image of example 2 of an electrolyte membrane of the invention based on PVDF-HFP and an ionic liquid;
FIG. 3 is an SEM image of example 3 of an electrolyte membrane of the invention based on PVDF-HFP and an ionic liquid;
Fig. 4 is an SEM image of example 4 of an electrolyte membrane of the invention based on PVDF-HFP and an ionic liquid.
The specific embodiment is as follows:
The invention is further described below in connection with examples, which should be construed as being limited to the scope of the invention as claimed.
The electrolyte membrane prepared by the invention can be characterized by the following method: the morphology of the electrode material produced can be scanned with a Scanning Electron Microscope (SEM).
Example 1
The electrolyte membrane based on PVDF-HFP and ionic liquid comprises polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, li salt and ionic liquid, wherein the specific proportions of the components are shown in the following table:
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) Weighing 7% of Li salt and 73% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain a Li salt-ionic liquid solution with the concentration of 0.5 mol/L;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 30min at the frequency of 25KHz and the power of 400W to obtain uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 127 ℃ for 10 hours;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
The electrolyte membrane based on PVDF-HFP and ionic liquid prepared as described above is shown in FIG. 1, from which it is seen: the electrolyte separator has high porosity, and the multi-hollow channels can add channels for Li + to transmit, thereby facilitating migration and conduction of Li +. The battery performance test shows that the electrolyte membrane based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 118.2 mAH.g -1 after the charge and discharge cycles of 0.1C current density are 100 times.
Example 2
The electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, li salt and ionic liquid, wherein the specific proportions of the components are shown in the following table:
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) Weighing 6% of Li salt and 69% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain about 0.5mol/L of Li salt-ionic liquid solution;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 50min at the frequency of 20KHz and the power of 450W to obtain uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 120 ℃ for 18 hours;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
The prepared electrolyte membrane based on PVDF-HFP and ionic liquid is shown in fig. 2, and can be seen from the figure: the electrolyte separator has high porosity, and the multi-hollow channels can add channels for Li + to transmit, thereby facilitating migration and conduction of Li +. The battery performance test shows that the electrolyte membrane based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 125.2 mAH.g -1 after the charge and discharge cycles of 0.1C current density are 100 times.
Example 3
The electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, li salt and ionic liquid, wherein the specific proportions of the components are shown in the following table:
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) Weighing 6% of Li salt and 64% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain 0.5mol/L of Li salt-ionic liquid solution;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 40min at the frequency of 26KHz and the power of 500W to obtain uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 125 ℃ for 12 hours;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
The prepared electrolyte membrane based on PVDF-HFP and ionic liquid is shown in fig. 3, and can be seen from the figure: the electrolyte separator has high porosity, and the multi-hollow channels can add channels for Li + to transmit, thereby facilitating migration and conduction of Li +. The battery performance test shows that the electrolyte membrane based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 135.2 mAH.g -1 after the charge and discharge cycles of 0.1C current density are 100 times.
Example 4:
the electrolyte membrane prepared based on PVDF-HFP and ionic liquid comprises polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder, li salt and ionic liquid, wherein the specific proportions of the components are shown in the following table:
The preparation method of the electrolyte membrane based on PVDF-HFP and ionic liquid comprises the following steps:
(1) Weighing 5% of Li salt and 60% of ionic liquid, and dissolving the Li salt in the ionic liquid to obtain 0.5mol/L of Li salt-ionic liquid solution;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion treatment for 45min at the frequency of 18KHz and the power of 550W to obtain uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 123 ℃ for 14 hours;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
The prepared electrolyte membrane based on PVDF-HFP and ionic liquid is shown in fig. 4, and can be seen from the figure: the electrolyte separator has high porosity, and the multi-hollow channels can add channels for Li + to transmit, thereby facilitating migration and conduction of Li +. The battery performance test shows that the electrolyte membrane based on PVDF-HFP and ionic liquid has good cycling stability, and the specific discharge capacity is 138.2 mAH.g -1 after the charge and discharge cycles of 0.1C current density are 100 times.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, i.e., the invention is not limited to the specific embodiments described herein, but is to be accorded the full scope of the claims.

Claims (9)

1. The electrolyte membrane based on PVDF-HFP and ionic liquid is characterized by comprising the following components in percentage by mass:
20-35% of polyvinylidene fluoride-hexafluoropropylene powder
60-73% Of ionic liquid
5-7% Of Li salt
The polyvinylidene fluoride-hexafluoropropylene powder is prepared from the following components in percentage by mass:
50-60% of polyvinylidene fluoride-hexafluoropropylene emulsion
3-10% Of anion-cation exchange resin
30-45% Of electrolyte
The preparation method comprises the following steps:
(1) Weighing anion-cation exchange resin and polyvinylidene fluoride-hexafluoropropylene emulsion according to the formula proportion, and mixing for 4-6 hours under the stirring action to form mixed emulsion;
(2) Filtering the mixed emulsion to obtain viscous polyvinylidene fluoride-hexafluoropropylene emulsion after adsorption;
(3) Dropwise adding electrolyte into the adsorbed polyvinylidene fluoride-hexafluoropropylene emulsion in a dropwise adding mode while stirring to prepare polyvinylidene fluoride-hexafluoropropylene gel;
(4) Drying polyvinylidene fluoride-hexafluoropropylene gel at 40-50 ℃;
(5) The dried polyvinylidene fluoride-hexafluoropropylene gel is ball-milled by a ball mill, and powder below 60 microns is screened out by a screen.
2. The electrolyte membrane of claim 1 wherein the ionic liquid is one of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide salt, 1-methyl-3-hexylimidazole fluoromethylsulfonylimide salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt.
3. The electrolyte membrane based on PVDF-HFP and an ionic liquid according to claim 2, wherein the Li salt is lithium bistrifluoromethylsulfonylimide.
4. The electrolyte membrane based on PVDF-HFP and ionic liquid according to claim 1, wherein the solid content of the polyvinylidene fluoride-hexafluoropropylene emulsion is 25-50%; the electrolyte is hydrochloric acid solution with the solution concentration of 0.1 mol/L.
5. The method for preparing an electrolyte membrane based on PVDF-HFP and ionic liquid according to claim 1, comprising the following steps:
(1) Weighing Li salt and ionic liquid according to the formula proportion, and dissolving the Li salt in the ionic liquid to obtain a salt-ionic liquid solution;
(2) Mixing the Li salt-ionic liquid solution with polyvinylidene fluoride-hexafluoropropylene powder, and performing ultrasonic dispersion for 30-50 min to obtain a uniform co-dispersion;
(3) Coating the co-dispersion on an aluminum foil through a film coater to form a film;
(4) Drying the film at 120-130 ℃ for 8-15h;
(5) The dried film was rapidly transferred into a glove box, where the film was peeled off to obtain an electrolyte membrane based on PVDF-HFP and an ionic liquid.
6. The method for preparing an electrolyte membrane based on PVDF-HFP and ionic liquid according to claim 5, wherein in step (1), the dissolution of Li salt in ionic liquid is performed in a glove box.
7. The method for preparing an electrolyte membrane based on PVDF-HFP and an ionic liquid according to claim 5, wherein in the step (2), the ultrasonic treatment is performed at a frequency of 10 to 30KHz and a power of 300 to 600W.
8. The method for preparing an electrolyte membrane based on PVDF-HFP and an ionic liquid according to claim 7, wherein in the step (2), the ultrasonic treatment has a frequency of 20KHz and a power of 450W.
9. The method for preparing an electrolyte membrane based on PVDF-HFP and an ionic liquid according to claim 5, wherein in step (4), the film is dried at 125 ℃ for 12 hours.
CN202111095615.3A 2020-09-17 2021-09-17 Electrolyte diaphragm based on PVDF-HFP and ionic liquid and preparation method thereof Active CN113839145B (en)

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KR100792713B1 (en) * 2006-09-21 2008-01-08 한국에너지기술연구원 Proton conducting electrolyte based on ionic liquid impregnated polymer with acidic counteranion and fuel cells using the same
CN101440188A (en) * 2008-12-30 2009-05-27 哈尔滨工业大学 Lithium ionic cell gel type ion liquid / polymer electrolyte and preparation thereof
CN101635380A (en) * 2009-07-15 2010-01-27 哈尔滨工业大学 Lithium ion battery gel type ionic liquid/polymer electrolyte and preparation method thereof
CN103840198A (en) * 2012-11-20 2014-06-04 中国科学院宁波材料技术与工程研究所 Lithium ion battery gel polymer electrolyte and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100792713B1 (en) * 2006-09-21 2008-01-08 한국에너지기술연구원 Proton conducting electrolyte based on ionic liquid impregnated polymer with acidic counteranion and fuel cells using the same
CN101440188A (en) * 2008-12-30 2009-05-27 哈尔滨工业大学 Lithium ionic cell gel type ion liquid / polymer electrolyte and preparation thereof
CN101635380A (en) * 2009-07-15 2010-01-27 哈尔滨工业大学 Lithium ion battery gel type ionic liquid/polymer electrolyte and preparation method thereof
CN103840198A (en) * 2012-11-20 2014-06-04 中国科学院宁波材料技术与工程研究所 Lithium ion battery gel polymer electrolyte and preparation method thereof

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