CN105914397B - Fluoropolymer electrolyte and its preparation method and application - Google Patents
Fluoropolymer electrolyte and its preparation method and application Download PDFInfo
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
Fluoropolymer electrolyte and its preparation method and application is birdsed of the same feather flock together polymer electrolyte and its synthetic method the present invention relates to novel fluorine, it is relatively low in order to solve the problem of the existing hygroscopic conductivity of the polymer dielectric containing polyoxyethylene structure.Fluoropolymer electrolyte of the present invention is formed by sodium p styrene sulfonate, polyethylene glycol methacrylate-styrene polymer, Hexafluorobutyl mathacrylate ternary polymerization, or by sodium p styrene sulfonate, polyethylene glycol methacrylate-styrene polymer, Hexafluorobutyl mathacrylate and vinylethylene carbonate is quarternary copolymerized forms, both the above fluoropolymer electrolyte can be also put into progress lithium salts displacement in lithium salt solution, and be applied to be used as electrolyte in all-solid lithium-ion battery.The present invention promotes the ionization of lithium ion, improves ionic conductivity, reduce the hydrophily of polymer, improve the mechanical performance of dielectric film by introducing strong electrophilic perfluoroalkyl in the structure.
Description
Technical field
Birds of the same feather flock together polymer electrolyte and its synthetic method the present invention relates to novel fluorine, and be related to full solid state polymer lithium from
Application in sub- battery.
Background technology
Full solid state polymer lithium ion battery is the high specific energy of new generation to grow up on the basis of liquid lithium ionic cell
Battery system, it is a kind of novel concept battery proposed for safety problem existing for solution liquid lithium ionic cell.Polyoxy
Ethylene (PEO) is as the most suitable matrix for preparing all solid state electrolyte generally acknowledged at present, and the polymer dielectric of the system is
Extensive research is obtained.
Recent studies indicate that influence of the structure of solid polymer electrolyte to performances such as its conductivity and mechanics
Significantly, the transference number of ions of solid polymer electrolyte is close to 1 (Hyukkeun Oh et al., Poly (arylene
ether)-Based Single-Ion Conductors for Lithium-Ion Batteries,Chem.Mater.2016,
28,188-196) it, and can also properly increase the mechanical performance of polymer.Current polymer dielectric conductivity compared with
Low, general conductivity at room temperature is 10-6~10-9Scm-1, it is impossible to reach the requirement of lithium ion battery.
And existing most of fluoropolymer-containing institutes that prepare using solvent are fluoride solvent, such preparation process into
This is higher.
Invention content
The purpose of the present invention is to solve the existing polymer dielectric containing polyoxyethylene structure is hygroscopic, conductivity
The problem of relatively low, and fluoropolymer electrolyte and its preparation method and application is provided.
The chemical structural formula of fluoropolymer electrolyte of the present invention is as follows：
Wherein X represents Na or Li.
The preparation method of fluoropolymer electrolyte I of the present invention is realized according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte
Ⅰ；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
Fluoropolymer electrolyte of the present invention is by sodium p styrene sulfonate, polyethylene glycol methacrylate-styrene polymer, first
Base hexafluorobutyl acrylate ternary polymerization forms.
The preparation method of fluoropolymer electrolyte II of the present invention is realized according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte
Ⅱ；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content in step 1, ethylene carbonate
Ethyl accounts for the 10%~15% of total reactant molar content.
Fluoropolymer electrolyte of the present invention is by sodium p styrene sulfonate, polyethylene glycol methacrylate-styrene polymer, first
Base hexafluorobutyl acrylate and vinylethylene carbonate is quarternary copolymerized forms.
The preparation method of fluoropolymer electrolyte III of the present invention is realized according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution
Carry out lithium salts displacement, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte III；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
The preparation method of fluoropolymer electrolyte IV of the present invention is realized according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution
Carry out lithium salts displacement, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte IV；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content in step 1, ethylene carbonate
Ethyl accounts for the 10%~15% of total reactant molar content.
The application of fluoropolymer electrolyte III and fluoropolymer electrolyte IV of the present invention is as all solid state lithium ion
Electrolyte in battery.
Fluoropolymer electrolyte III and IV of the present invention uses Sulfonic Lithium as lithium source, and in polymer architecture
Middle to introduce strong electrophilic perfluoroalkyl, the charge for making sulfonic group anion is further delocalized, promotes the ionization of lithium ion, carries
The conductivity of high ionic conductivity, fluoropolymer electrolyte III and fluoropolymer electrolyte IV reaches 8 × 10-6S/cm with
On.
At present solid polymer electrolyte mainly by Sulfonic Lithium as lithium source and PEO as matrix, the present invention passes through introducing
The structure of perfluoroalkyl can not only increase the conductivity of polymer dielectric, can also reduce the hydrophily of polymer, optimization
The mechanical performance of polymer dielectric film.
The present invention is synthesized, and preparation condition is mild using a series of not fluorine-containing solvents.The present invention passes through free radical
Reaction introduces ethylene carbonate ester structure on main polymer chain, and ethylene carbonate ester structure energy solvation and transmission lithium ion reduce
Interionic interacts, and improves the conductivity of polymer dielectric.
Description of the drawings
Fig. 1 is the infrared spectrogram of fluoropolymer electrolyte I that embodiment one obtains；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of fluoropolymer electrolyte I that embodiment one obtains；
Fig. 3 is the conductivity test chart of fluoropolymer electrolyte I that embodiment one obtains；
Fig. 4 is the stress-strain curve of fluoropolymer electrolyte I that embodiment one obtains；
Fig. 5 is the infrared spectrogram of fluoropolymer electrolyte II that embodiment two obtains；
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of fluoropolymer electrolyte II that embodiment two obtains；
Fig. 7 is the conductivity test chart of fluoropolymer electrolyte II that embodiment two obtains；
Fig. 8 is the stress-strain curve of fluoropolymer electrolyte II that embodiment two obtains；
Fig. 9 is the conductivity test chart of fluoropolymer electrolyte III that embodiment three obtains；
Figure 10 is the conductivity test chart of fluoropolymer electrolyte IV that example IV obtains.
Specific embodiment
Specific embodiment one：The preparation method of present embodiment fluoropolymer electrolyte I is implemented according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte
Ⅰ；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
Present embodiment poly (sodium 4-styrenesulfonate)-polyethylene glycol methacrylate-styrene polymer-Hexafluorobutyl mathacrylate
Reaction equation is as follows：
Specific embodiment two：The preparation method of present embodiment fluoropolymer electrolyte II is implemented according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte
Ⅱ；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content in step 1, ethylene carbonate
Ethyl accounts for the 10%~15% of total reactant molar content.
Present embodiment poly (sodium 4-styrenesulfonate)-polyethylene glycol methacrylate-styrene polymer-Hexafluorobutyl mathacrylate-carbon
The reaction equation of sour vinylethylene is as follows：
Specific embodiment three：The preparation method of present embodiment fluoropolymer electrolyte III is implemented according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution
Carry out lithium salts displacement, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte III；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
Present embodiment step 3 removes NaCl and extra LiCl using dialysis process, purges until solution is sticky.
Step 4 polymer dielectric is dissolved in a concentration of 0.1g/mL during N,N-dimethylformamide.
Specific embodiment four：The preparation method of present embodiment fluoropolymer electrolyte IV is implemented according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol
Methacrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added after ten minutes
Hexafluorobutyl mathacrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution
Carry out lithium salts displacement, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte IV；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content in step 1, ethylene carbonate
Ethyl accounts for the 10%~15% of total reactant molar content.
Specific embodiment five：It is molten in step 1 unlike one of present embodiment and specific embodiment one to four
Agent is deionized water, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N, N- dimethyl pyrrolidone.Other steps and
One of parameter and specific embodiment one to four are identical.
Specific embodiment six：Initiator in present embodiment step 1 unlike specific embodiment one or three
For ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide or azodiisobutyronitrile.Other steps and parameter and specific embodiment one
Or three is identical.
Specific embodiment seven：Initiator in present embodiment step 1 unlike specific embodiment two or four
For ammonium persulfate or azodiisobutyronitrile.Other steps and parameter are identical with specific embodiment two or four.
Specific embodiment eight：Lithium salt solution in present embodiment step 2 unlike specific embodiment three or four
A concentration of 0.5g/mL.Other steps and parameter are identical with specific embodiment three or four.
Specific embodiment nine：It is described unlike one of present embodiment and specific embodiment one to four to be dried to
The process of film process is as follows：First dry 6~8 hours at 70~80 DEG C, 50~60 DEG C of dryings 6~8 hours are then cooled to, most
After be cooled to 40 DEG C of drying and forming-films.Other steps and one of parameter and specific embodiment one to four are identical.
Specific embodiment ten：It is described unlike one of present embodiment and specific embodiment one to four to be dried to
The process of film process is as follows：Under vacuum, it is dried 24~72 hours with 80 DEG C of Temperature Vacuum.Other steps and parameter with
One of specific embodiment one to four is identical.
Specific embodiment 11：Drying and forming-film obtains unlike one of present embodiment and specific embodiment one to four
The thickness of the fluoropolymer electrolyte arrived is 0.5~20mm.Other steps and one of parameter and specific embodiment one to four
It is identical.
Embodiment one：The preparation method of the present embodiment fluoropolymer electrolyte I is implemented according to the following steps：
First, it is 1 according to molar ratio in the case where inert nitrogen gas protects atmosphere:2 by 1.374g sodium p styrene sulfonates and 6g
Polyethylene glycol methacrylate-styrene polymer is added in 40mLDMF solvents, initiator azodiisobutyronitrile 84mg is then added in, at 80 DEG C
At a temperature of react and add 0.265ml Hexafluorobutyl mathacrylates after ten minutes, the reaction was continued 20 minutes, obtains polymerization production
Object；
2nd, polymerizate is cast in Teflon mould, is handled under vacuum with 80 DEG C of drying and forming-films
To fluoropolymer electrolyte I.
Poly (sodium 4-styrenesulfonate)-polyethylene glycol methacrylate-styrene polymer-methacrylic acid six that the present embodiment is prepared
Fluorine butyl ester Electrolyte film thickness is 18mm, and conductivity is 3.51 × 10-7S·cm-1, fracture strength 1.62MPa.
The test method of wherein conductivity is as follows：The dielectric film being prepared is added between two copper electrodes, is formed
Polymer dielectric blocking electrode system, does ac impedance measurement, obtains the complex impedance plane figure of polymer film, curve is in high frequency
The intersection value of area and horizontal axis is ontology impedance.According to ontology impedance (Rb) relationship between ionic conductivity (σ):σ=d/
(S*Rb), ionic conductivity is calculated, wherein d is the thickness of polymer dielectric film, S is polymer dielectric dielectric film
With the contact area of electrode.
Embodiment two：The preparation method of the present embodiment fluoropolymer electrolyte II is implemented according to the following steps：
First, it is 1 according to molar ratio in the case where inert nitrogen gas protects atmosphere:2 by 0.687g sodium p styrene sulfonates with
4.535g polyethylene glycol methacrylate-styrene polymers are added in 40mLDMF solvents, then add in initiator azodiisobutyronitrile 50mg,
It is reacted at a temperature of 80 DEG C and adds 0.375ml Hexafluorobutyl mathacrylates after ten minutes, add in vinylethylene carbonate
0.171ml then proceedes to reaction and obtains polymerizate in 20 minutes；
2nd, polymerizate is cast in Teflon mould, is handled under vacuum with 80 DEG C of drying and forming-films
To fluoropolymer electrolyte II.
Poly (sodium 4-styrenesulfonate)-polyethylene glycol methacrylate-styrene polymer-methacrylic acid six that the present embodiment is prepared
Fluorine butyl ester-vinylethylene carbonate Electrolyte film thickness is 12mm, and conductivity is 1.25 × 10-6S·cm-1, fracture strength is
1.38MPa。
Embodiment three：The preparation method of the present embodiment fluoropolymer electrolyte III is implemented according to the following steps：
First, the polymerizate obtained by step 1 in embodiment one is added to progress lithium salts in lithium salts (LiCl) solution and puts
It changes, the solution after being replaced；
2nd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
3rd, the polymer dielectric for the drying for obtaining step 2 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte film III.
Poly- p styrene sulfonic acid lithium-polyethylene glycol methacrylate-styrene polymer-methacrylic acid six that the present embodiment is prepared
Fluorine butyl ester Electrolyte film thickness is 10mm, and conductivity is 8.32 × 10-6S·cm-1。
Example IV：The preparation method of the present embodiment fluoropolymer electrolyte IV is implemented according to the following steps：
First, the polymerizate obtained by step 1 in embodiment two is added to progress lithium salts displacement in lithium salt solution, obtains
Solution after displacement；
2nd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain drying
Polymer dielectric；
3rd, the polymer dielectric for the drying for obtaining step 2 is dissolved in n,N-Dimethylformamide, is then cast
In Teflon mould, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte film IV.
Poly- p styrene sulfonic acid lithium-polyethylene glycol methacrylate-styrene polymer-methacrylic acid six that the present embodiment is prepared
Fluorine butyl ester-vinylethylene carbonate Electrolyte film thickness is 10mm, and conductivity is 8.49 × 10-6S·cm-1。
Claims (10)
1. fluoropolymer electrolyte, it is characterised in that the chemical structural formula of the fluoropolymer electrolyte is as follows：
Wherein X represents Na or Li.
2. the preparation method of fluoropolymer electrolyte, it is characterised in that be to realize according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol methyl
Acrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added methyl after ten minutes
Hexafluorobutyl acrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte I；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
3. the preparation method of fluoropolymer electrolyte, it is characterised in that be to realize according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol methyl
Acrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added methyl after ten minutes
Hexafluorobutyl acrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, polymerizate is cast in Teflon mould, drying and forming-film handles to obtain fluoropolymer electrolyte II；
Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content wherein in step 1, ethylene carbonate Asia second
Ester accounts for the 10%~15% of total reactant molar content.
4. the preparation method of fluoropolymer electrolyte, it is characterised in that be to realize according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol methyl
Acrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added methyl after ten minutes
Hexafluorobutyl acrylate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution and is carried out
Lithium salts is replaced, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain dry polymerization
Object electrolyte；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast in poly-
In Teflon mold, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte III；
Wherein Hexafluorobutyl mathacrylate accounts for the 10%~30% of total reactant molar content in step 1.
5. the preparation method of fluoropolymer electrolyte, it is characterised in that be to realize according to the following steps：
First, it is 1 according to molar ratio under inert gas shielding atmosphere:1~3 by sodium p styrene sulfonate and polyethylene glycol methyl
Acrylate is added in solvent, then adds in initiator, is reacted at a temperature of 70~80 DEG C and is added methyl after ten minutes
Hexafluorobutyl acrylate and vinylethylene carbonate, the reaction was continued 15~30 minutes, obtains polymerizate；
2nd, LiCl is added in deionized water, obtains lithium salt solution, then polymerizate is added in lithium salt solution and is carried out
Lithium salts is replaced, the solution after being replaced；
3rd, it dialyses to the solution after displacement, then is placed in vacuum drying oven and is dried through purging, obtain dry polymerization
Object electrolyte；
4th, the polymer dielectric for the drying for obtaining step 3 is dissolved in n,N-Dimethylformamide, is then cast in poly-
In Teflon mold, solvent is removed at 40 DEG C, drying and forming-film handles to obtain fluoropolymer electrolyte IV；
Hexafluorobutyl mathacrylate accounts for the 10%~15% of total reactant molar content wherein in step 1, ethylene carbonate Asia second
Ester accounts for the 10%~15% of total reactant molar content.
6. according to the preparation method of claim 2 to 5 any one of them fluoropolymer electrolyte, it is characterised in that step 1
In solvent be deionized water, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N, N- dimethyl pyrrolidone.
7. according to the preparation method of claim 2 to 5 any one of them fluoropolymer electrolyte, it is characterised in that step 1
In initiator be ammonium persulfate, potassium peroxydisulfate, benzoyl peroxide or azodiisobutyronitrile.
8. the preparation method of fluoropolymer electrolyte according to claim 4 or 5, it is characterised in that lithium salts in step 2
A concentration of 0.5g/mL of solution.
9. according to the preparation method of claim 2 to 5 any one of them fluoropolymer electrolyte, it is characterised in that be dried to
The thickness for the fluoropolymer electrolyte that film obtains is 0.5~20mm.
10. the application for the fluoropolymer electrolyte that preparation method is prepared, feature exist as described in claim 4 or 5
In using fluoropolymer electrolyte as the electrolyte in all-solid lithium-ion battery.
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| WO2024121517A1 (en) * | 2022-12-08 | 2024-06-13 | Centre National De La Recherche Scientifique (Cnrs) | Solid polymer electrolyte comprising at least one polymer comprising at least one unit obtained from a styrenic monomer and a specific polymer |
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| CN106711503A (en) * | 2016-12-19 | 2017-05-24 | 西南石油大学 | Single-ion gel polymer electrolyte and preparation method thereof |
| CN109004280B (en) * | 2018-07-11 | 2021-06-08 | 珠海冠宇电池股份有限公司 | Preparation method of all-solid-state polymer electrolyte and all-solid-state polymer battery |
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| CN109888385B (en) * | 2019-01-25 | 2020-11-06 | 厦门大学 | Electrolyte for lithium metal secondary battery and lithium metal secondary battery |
| CN110034331A (en) * | 2019-04-28 | 2019-07-19 | 南开大学 | A kind of NEW TYPE OF COMPOSITE polymer dielectric and its preparation method and application |
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| CN114566699B (en) * | 2022-01-15 | 2024-02-27 | 西安理工大学 | Fluorine-containing composite lithium ion solid electrolyte and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425629C (en) * | 2001-10-17 | 2008-10-15 | 三星Sdi株式会社 | Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte |
| JP2012209145A (en) * | 2011-03-30 | 2012-10-25 | Sekisui Chem Co Ltd | Lithium-ion secondary battery |
| CN103265721A (en) * | 2013-04-28 | 2013-08-28 | 华中科技大学 | Gel electrolyte based on porous matrix and resisting electrolyte leakage and preparation method thereof |
-
2016
- 2016-06-28 CN CN201610487646.6A patent/CN105914397B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425629C (en) * | 2001-10-17 | 2008-10-15 | 三星Sdi株式会社 | Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte |
| JP2012209145A (en) * | 2011-03-30 | 2012-10-25 | Sekisui Chem Co Ltd | Lithium-ion secondary battery |
| CN103265721A (en) * | 2013-04-28 | 2013-08-28 | 华中科技大学 | Gel electrolyte based on porous matrix and resisting electrolyte leakage and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024121517A1 (en) * | 2022-12-08 | 2024-06-13 | Centre National De La Recherche Scientifique (Cnrs) | Solid polymer electrolyte comprising at least one polymer comprising at least one unit obtained from a styrenic monomer and a specific polymer |
| FR3143037A1 (en) * | 2022-12-08 | 2024-06-14 | Centre National De La Recherche Scientifique (Cnrs) | Solid polymer electrolyte comprising at least one polymer comprising at least one unit obtained from a styrenic monomer and a particular polymer |
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