CN106450474A - Gelled polymer electrolyte membrane and preparation method thereof - Google Patents
Gelled polymer electrolyte membrane and preparation method thereof Download PDFInfo
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- CN106450474A CN106450474A CN201610976877.3A CN201610976877A CN106450474A CN 106450474 A CN106450474 A CN 106450474A CN 201610976877 A CN201610976877 A CN 201610976877A CN 106450474 A CN106450474 A CN 106450474A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a gelled polymer electrolyte membrane and a preparation method thereof. The preparation method comprises the steps that a copolymer of polyvinylidene fluoride and hexafluoropropylene is added into graphene oxide dispersed into N,N-dimethylformamide to form sol, a membrane is prepared and then soaked in an electrolyte, and the gelled polymer electrolyte membrane is obtained. According to the gelled polymer electrolyte membrane and the preparation method thereof, operation is easy, and the polymer electrolyte membrane prepared through the method is uniform and smooth in surface, has the high heat stability, has the high ionic conductivity at room temperature and has the application prospect of serving as a lithium ion battery gelled electrolyte material.
Description
Technical field
The present invention relates to a kind of technology of field of lithium ion battery, the enhanced gel of specifically a kind of graphene oxide
Type polymer dielectric film and preparation method thereof.
Background technology
The specific energy density of lithium ion battery Yin Qigao, wide electrochemical operation window and using temperature range and to ring
The significantly advantage such as border close friend, has a wide range of applications, for example mobile phone, camera and computer in people's daily life, but also
To the extension of more fields, the such as vehicles, medical apparatus and instruments and Space Science and Technology.
Traditional liquid electrolyte is the organic solution system containing lithium salts, and this makes assembled lithium ion battery grow
Time using or high temperature in the case of electrolyte leakage, the short circuit even danger of blast easily occur.Accordingly, as succedaneum, have
The polymer dielectric having greater security energy arises at the historic moment.
Polymeric matrix is the core component of gel polymer electrolyte, has the polymer of certain microcellular structure
Network, plays the effect of support frame, and lithium ion passes through electrolyte conduction in microcellular structure for the absorption.At present, polymer matrix
The research of body is concentrated mainly on polyoxyethylene (PEO), polymethyl acrylate (PMMA), polyacrylonitrile (PAN) and Kynoar
(PVDF) and Kynoar and hexafluoropropene copolymer (PVDF HFP).Gel-type polymer electrolyte plays barrier film effect
While also there is preferable lithium ion conductivity and mechanical property, can be applicable to prepare the lithium of safe and reliable and function admirable from
Sub- battery.
However, polymer dielectric there is also some needs to improve local, such as ionic conductance, lithium ion conductivity and
Mechanical performance.Ionic conductance is as the most important factor weighing polymer dielectric, the always emphasis of researcher concern.Arrive
Mainly there is the method that two classes are improved so far：The first kind be the crosslinking carrying out physics or chemistry with other macromolecular materials altogether
Mixed, Equations of The Second Kind is doping organic or inorganic additive.
Content of the invention
The present invention is directed to prior art and requires the relatively low defect of ionic conductance under larger and room temperature to the amount of additive, carries
Go out a kind of gel-type polymer electrolyte film and preparation method thereof, the present invention is simple to operate, the film preparing is uniformly and surface
Smooth, there is high heat stability, have high ionic conductance at room temperature, have and be used as lithium ion battery gel type electrolyte
The application prospect of material.
The present invention is achieved by the following technical solutions：
The present invention relates to a kind of preparation method of gel-type polymer electrolyte film, by being scattered in N, N dimethyl methyl
Add the copolymer (PVDF HFP) of Kynoar and hexafluoropropene thus shape in graphene oxide (GO) in amide (DMF)
Become colloidal sol, through masking and be soaked in electrolyte and obtain gel-type polymer electrolyte.
The preferred purity of described graphene oxide>99wt%, monolayer rate>99%, trans D is 0.5 μm～10 μm.
Described Kynoar is about 455000 with the weight average molecular weight of the copolymer of hexafluoropropene, and number-average molecular weight is about
For 110000, density is 1.77g/mL.
Described graphene oxide, N, the quality of the copolymer of N dimethylformamide, Kynoar and hexafluoropropene
Than for 0.5: 1: 300～1.5: 1: 200.
Described dispersion refers to：Add graphene oxide into N, in N dimethylformamide, first magnetic agitation 20～
40min, more ultrasonic 20～40min, altogether repeat 3～5 times, so that graphene oxide is disperseed in N, N dimethylformamide all
Even.
Described interpolation refers to：Being scattered in N, add in the graphene oxide of N dimethylformamide Kynoar with
The copolymer of hexafluoropropene, 30 DEG C～50 DEG C water-bath magnetic agitation 3～5h make Kynoar equal with the copolymer of hexafluoropropene
Even dissolving.
Described masking refers to：Described colloidal sol is stood after 20～40min under 30 DEG C～50 DEG C environment, with scraper by its
Coating on a glass, puts in climatic chamber just film forming 5min～1h, be then immersed at once 30 DEG C～50 DEG C go from
Phase transfer 10min～2h in sub- water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, obtains polymer
Film.
Described climatic chamber is preferably provided with temperature and is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%.
The group of described electrolyte is divided into：Lithium hexafluoro phosphate ethylene carbonate, dimethyl carbonate and Ethyl methyl carbonate, its
Volume ratio is 1: 1: 1.
Described immersion refers to：The polymeric film that masking is obtained is cut into disk, transfers to the glove full of high-purity argon gas
In case, soak 10min～2h in the electrolytic solution, that is, obtain gel-type polymer electrolyte film.
The present invention relates to the polymer dielectric film that said method prepares, its heat decomposition temperature is 422 DEG C, pick up
For 372%.The present invention relates to the gel-type polymer electrolyte that said method prepares, its ionic conductance at normal temperatures
For 2.024mS/cm, electrochemical stability window is 4.6V.
Technique effect
Compared with prior art, the present invention process simple used time is short, once dispersion, add, after masking and immersion
To gel-type polymer electrolyte, and without pyroreaction, energy saving；Additionally, the graphene oxide needed for the present invention is former
Material is few, and graphene oxide is only 1.667 × 10 with the mass ratio of Kynoar and the copolymer of hexafluoropropene‐3～7.5
×10‐3：And the present invention need not add surfactant, reducing agent and oxidant, low production cost in preparation process；Separately
Outward, the addition of graphene oxide reduces the degree of crystallinity of Kynoar and the copolymer of hexafluoropropene, can be obviously improved solidifying
The ionic conductance of glue-type polymer dielectric and the high rate performance of institute's assembled battery.
Brief description
Fig. 1 is the field emission scanning electron microscope figure of the polymeric dielectric film of preparation in embodiment 1；
Fig. 2 is the electrochemical impedance spectrogram that the gel-type polymer electrolyte prepared in embodiment 1 is tested at room temperature；
Fig. 3 is that the multiplying power discharging of the simulated battery of the gel-type polymer electrolyte assembling using preparation in embodiment 1 is bent
Line chart.
Specific embodiment
Embodiment 1
The present embodiment comprises the following steps：The graphene oxide of 5mg is added the N of 10mg, in N dimethylformamide, first
Magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl methyl
The copolymer of 2g Kynoar and hexafluoropropene, 30 DEG C～50 DEG C water-bath magnetic agitation 3～5h are added in amide homogeneous solution
Make the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and hexafluoro
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of propylene, it is coated with a glass with scraper, is put into constant temperature permanent
First film forming 10min in wet tank (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), be then immersed at once 30 DEG C～
Phase transfer 1h in 50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, is polymerized
Thing film.As shown in figure 1, the polymer dielectric film surfacing prepared in aforementioned manners, there is the structure that hole enriches.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF62h in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By above-mentioned gel-type polymer electrolyte according to the assembling mode of sandwich, it is assembled into rustless steel steel disc/polymer
Electrolyte/rustless steel steel disc symmetrically blocks simulated battery, at room temperature after standing 1h, using the PGSTAT of Merohm company of Switzerland
302N type electrochemical workstation tests electrochemical impedance spectroscopy, as shown in Figure 2.
The electrical conductivity of described gel-type polymer electrolyteR in formulab, d and S respectively bulk resistance, thickness
And area.Being calculated the gel-type polymer electrolyte of the present embodiment ionic conductance at room temperature is 2.024mS/cm.
By positive electrode LiFePO4, conductive agent acetylene black and binding agent Kynoar in mass ratio 8: 1: 1 uniformly mix
Close, add solvent N methyl pyrrolidone, stirring uniformly muddy, be coated uniformly on aluminium foil with scraper, then vacuum is done
Dry 10～14h, punching becomes the disk positive pole of diameter 10mm.With lithium metal as negative pole, above-mentioned gel-type polymer electrolyte be every
Film and electrolyte, are assembled into CR 2016 type button cell in the glove box full of high-purity argon gas.Use after standing 10～14h
The LAND CT 2001A battery test system of Wuhan Land Electronic Co., Ltd., in the voltage range of 2.5V～4.2V
Interior, carry out charge-discharge performance test with different charge-discharge magnifications (0.1C, 0.2C, 0.5C, 1C and 2C).As shown in Figure 3.Discharge and recharge
Loop test result shows, the specific discharge capacity of 0.1C and 2C is about 165mAh/g and 52mAh/g.
Embodiment 2
The present embodiment comprises the following steps：The graphene oxide of 7.5mg is added the N of 10mg, in N dimethylformamide,
First magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl
The copolymer of 2g Kynoar and hexafluoropropene is added in Methanamide homogeneous solution, 30 DEG C～50 DEG C water-bath magnetic agitation 3～
5h makes the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and six
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of fluoropropene, it is coated with a glass with scraper, is put into constant temperature
First film forming 10min in constant humidity cabinet (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), is then immersed in 30 DEG C at once
Phase transfer 1h in～50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, is gathered
Compound film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF62h in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 2.221mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 161mAh/g and 105mAh/g.
Embodiment 3
The present embodiment comprises the following steps：The graphene oxide of 15mg is added the N of 10mg, in N dimethylformamide,
First magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl
The copolymer of 2g Kynoar and hexafluoropropene is added in Methanamide homogeneous solution, 30 DEG C～50 DEG C water-bath magnetic agitation 3～
5h makes the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and six
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of fluoropropene, it is coated with a glass with scraper, is put into constant temperature
First film forming 10min in constant humidity cabinet (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), is then immersed in 30 DEG C at once
Phase transfer 1h in～50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, is gathered
Compound film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF610min in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 1.797mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 150mAh/g and 41mAh/g.
Embodiment 4
The present embodiment comprises the following steps：The graphene oxide of 50mg is added the N of 100mg, in N dimethylformamide,
First magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl
The copolymer of 30g Kynoar and hexafluoropropene is added in Methanamide homogeneous solution, 30 DEG C～50 DEG C water-bath magnetic agitation 3～
5h makes the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and six
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of fluoropropene, it is coated with a glass with scraper, is put into constant temperature
First film forming 10min in constant humidity cabinet (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), is then immersed in 30 DEG C at once
Phase transfer 1h in～50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, is gathered
Compound film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF62h in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 1.264mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 144mAh/g and 16mAh/g.
Embodiment 5
The present embodiment comprises the following steps：The graphene oxide of 5mg is added the N of 10mg, in N dimethylformamide, first
Magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl methyl
The copolymer of 2g Kynoar and hexafluoropropene, 30 DEG C～50 DEG C water-bath magnetic agitation 3～5h are added in amide homogeneous solution
Make the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and hexafluoro
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of propylene, it is coated with a glass with scraper, is put into constant temperature permanent
First film forming 5min in wet tank (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), be then immersed at once 30 DEG C～
Phase transfer 10min in 50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, obtains
Polymeric film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF62h in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 1.735mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 158mAh/g and 45mAh/g.
Embodiment 6
The present embodiment comprises the following steps：The graphene oxide of 5mg is added the N of 10mg, in N dimethylformamide, first
Magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N dimethyl methyl
The copolymer of 2g Kynoar and hexafluoropropene, 30 DEG C～50 DEG C water-bath magnetic agitation 3～5h are added in amide homogeneous solution
Make the copolymer uniform dissolution of Kynoar and hexafluoropropene.By the Kynoar of above-mentioned graphene oxide doped and hexafluoro
After 30 DEG C～50 DEG C standing 20～40min of the copolymer colloidal sol of propylene, it is coated with a glass with scraper, is put into constant temperature permanent
First film forming 1h in wet tank (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), is then immersed in 30 DEG C～50 at once
DEG C deionized water in phase transfer 2h.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven, that is, obtains polymer
Film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF62h in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 1.852mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 160mAh/g and 49mAh/g.
Embodiment 7
The present embodiment comprises the following steps：The graphene oxide of 150mg is added the N of 100mg, N dimethylformamide
In, first magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times altogether.In the N of above-mentioned graphene oxide, N bis-
The copolymer of 20g Kynoar and hexafluoropropene is added, 30 DEG C～50 DEG C water-bath magnetic force stir in methylformamide homogeneous solution
Mixing 3～5h makes the copolymer uniform dissolution of Kynoar and hexafluoropropene.Polyvinylidene fluoride by above-mentioned graphene oxide doped
Alkene is stood after 20～40min with 30 DEG C～50 DEG C of the copolymer colloidal sol of hexafluoropropene, is coated with a glass with scraper, puts
Enter first film forming 1h in climatic chamber (temperature is 20 DEG C～30 DEG C～50 DEG C, and humidity is 60～70%), be then immersed at once
Phase transfer 10min in 30 DEG C～50 DEG C of deionized water.Then 10～14h is dried in 50 DEG C～70 DEG C of vacuum drying oven,
Obtain polymeric film.
Above-mentioned dielectric film is cut into the disk of diameter 16mm, transfers to full of in the glove box of high-purity argon gas, be immersed in
1.0M LiPF610min in the electrolyte of EC/DMC/EMC (1: 1: 1, v/v/v), that is, obtain gel-type polymer electrolyte film.
By electrochemical impedance spectroscopy test is carried out to above-mentioned polymer dielectric film, and it is calculated gel-type polymer electricity
Solution matter ionic conductance at room temperature is 1.681mS/cm.
Charge and discharge cycles test is carried out further to above-mentioned polymer dielectric film, result shows：The electric discharge of 0.1C and 2C
Specific capacity is about 143mAh/g and 37mAh/g.
Above-mentioned be embodied as can by those skilled in the art on the premise of without departing substantially from the principle of the invention and objective with difference
Mode local directed complete set is carried out to it, protection scope of the present invention is defined by claims and is not embodied as institute by above-mentioned
Limit, each implementation in the range of it is all by the constraint of the present invention.
Claims (10)
1. a kind of preparation method of gel-type polymer electrolyte film is it is characterised in that by being scattered in N, N dimethyl methyl
Add the copolymer of Kynoar and hexafluoropropene thus forming colloidal sol, through masking and soak in graphene oxide in amide
Gel-type polymer electrolyte film is obtained in electrolyte.
2. preparation method according to claim 1, is characterized in that, described graphene oxide purity>99wt%, monolayer rate
>99%, trans D is 0.5 μm～10 μm.
3. preparation method according to claim 1, is characterized in that, described graphene oxide, N, N dimethylformamide,
Kynoar is 0.5: 1: 300～1.5: 1: 200 with the mass ratio of the copolymer of hexafluoropropene.
4. preparation method according to claim 1, is characterized in that, described dispersion refers to：Add graphene oxide into N,
In N dimethylformamide, first magnetic agitation 20～40min, more ultrasonic 20～40min, repeat 3～5 times, make graphene oxide
N, N dimethylformamide are uniformly dispersed.
5. preparation method according to claim 1, is characterized in that, described interpolation refers to：It is being scattered in N, N dimethyl
The copolymer of Kynoar and hexafluoropropene, 30 DEG C～50 DEG C water-bath magnetic agitation 3 are added in the graphene oxide of Methanamide
～5h makes the copolymer uniform dissolution of Kynoar and hexafluoropropene.
6. preparation method according to claim 1, is characterized in that, described masking refers to：By described colloidal sol 30 DEG C～
After standing 20～40min under 50 DEG C of environment, it is coated with a glass with scraper, put into first film forming 5min in climatic chamber
～1h, is then immersed in phase transfer 10min～2h in 30 DEG C～50 DEG C of deionized water at once.Then true at 50 DEG C～70 DEG C
10～14h is dried in empty drying baker, that is, obtains polymeric film.
7. preparation method according to claim 1, is characterized in that, described climatic chamber setting temperature is 20 DEG C～30
DEG C～50 DEG C, humidity is 60～70%.
8. preparation method according to claim 1, is characterized in that, the group of described electrolyte is divided into：Lithium hexafluoro phosphate carbon
Vinyl acetate, dimethyl carbonate and Ethyl methyl carbonate, its volume ratio is 1: 1: 1.
9. preparation method according to claim 1, is characterized in that, described immersion refers to：The polymer that masking is obtained
Film is cut into disk, transfers to full of in the glove box of high-purity argon gas, soaks 10min～120min in the electrolytic solution, that is, coagulated
Glue-type polymer dielectric film.
10. a kind of gel-type polymer electrolyte film is it is characterised in that prepare according to methods described arbitrary in claim 19
Obtain, the heat decomposition temperature of this gel-type polymer electrolyte film is 422 DEG C, pick up is 372%；Ionic conductance is more than
The specific discharge capacity of 1.681mS/cm, 0.1C and 2C is more than 143mAh/g and 16mAh/g, and electrochemical stability window is 4.6V.
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| CN109244540A (en) * | 2018-11-19 | 2019-01-18 | 中国科学院宁波材料技术与工程研究所 | A kind of solid polymer electrolyte, preparation method and lithium ion battery |
| CN110176629A (en) * | 2019-03-07 | 2019-08-27 | 苏州大学 | A kind of graphene oxide modified polymer gel electrolyte and sodium metal battery |
| CN111769323A (en) * | 2020-07-16 | 2020-10-13 | 凤凰新能源(惠州)有限公司 | High-hardness polymer battery cell and preparation method thereof |
| CN112542611A (en) * | 2019-09-20 | 2021-03-23 | 北京石墨烯研究院 | Composition for gel electrolyte, flexible battery and preparation method thereof |
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