CN113078352B - Solvent and porous carbon reinforced composite polymer electrolyte and method thereof - Google Patents
Solvent and porous carbon reinforced composite polymer electrolyte and method thereof 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
- 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
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Abstract
The invention relates to a solvent and porous carbon reinforced composite polymer electrolyte and a preparation method thereof, belonging to the field of solid electrolyte preparation. The method comprises the following steps: mixing poly (vinylidene fluoride-co-hexafluoropropylene), lithium salt and an additive, and adding the mixture into a solvent to obtain a mixed solution A; ultrasonically dispersing porous carbon powder into a solvent to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain precursor slurry; and (4) defoaming the precursor slurry in a vacuum defoaming machine, and transferring to a mold for drying. The solvated lithium ions of the invention are used as carriers of the polymer electrolyte, and simultaneously play a role of a plasticizer, thereby greatly improving the ionic conductivity of the polymer. However, higher concentrations of solvated lithium ions significantly degrade the mechanical properties of the polymer electrolyte. The combination of the porous carbon obviously enhances the mechanical strength and the processability of the polymer electrolyte under the condition of not losing the high ionic conductivity of the polymer electrolyte.
Description
Technical Field
The invention relates to a solvent and porous carbon reinforced composite polymer electrolyte and a preparation method thereof, belonging to the field of solid electrolyte preparation.
Background
Lithium metal is the best anode material for known lithium-based battery technologies, having the highest volumetric and highest gravimetric energy densities. However, the side reactions present in lithium batteries, along with the flammability and leakage problems of flammable organic liquid electrolytes, still pose a safety hazard for their use in electric vehicles. In order to overcome the above-mentioned problems of the liquid electrolyte in the lithium metal battery, research on the solid electrolyte has been increasingly conducted in recent years instead of the liquid electrolyte. The challenges of polymer electrolytes for lithium batteries are mainly due to poor ionic conductivity. The polymer electrolyte generally combines with lithium ions through polymer segmental motion of an amorphous region, dissociates and transmits ions, and the inherent property greatly limits the ionic conductivity of the common polymer electrolyte, thereby limiting the practical application of the common polymer electrolyte. In order to meet the actual demand, polymer/inorganic material composite electrolytes (CPEs) and Gel Polymer Electrolytes (GPEs) have been widely designed and developed. The composite polymer electrolyte is designed to combine the advantages of different materials and overcome the disadvantages of a single system. Composite electrolytes generally include polymer-inert filler composite electrolytes and polymer-active ceramic composite electrolytes. In addition, the gel electrolyte is also a common composite electrolyte, controllable and non-leakage liquid or liquid electrolyte is added into a polymer matrix, the ionic conductivity is improved by fusing the advantages of small molecular organic matters and sacrificing the mechanical property of the material, and the performance and safety of the battery can also be improved, so that the gel electrolyte draws wide attention.
Disclosure of Invention
The invention aims to provide a solvent and porous carbon reinforced composite polymer electrolyte with high safety and excellent electrochemical performance and a method thereof, aiming at the defects of the prior art. The porous carbon is used as the mechanical filler from the perspective of enhancing the lithium ion conductivity of the polymer matrix by the solvated lithium ions, so that the problems of low ionic conductivity, poor stability, complex preparation process and the like of the traditional polymer electrolyte are solved, and the preparation of the composite polymer electrolyte with high ionic conductivity is realized.
The invention adopts the following specific technical scheme:
on the one hand, the invention provides a preparation method of a solvent and porous carbon reinforced composite polymer electrolyte, which comprises the following specific steps:
s1: mixing the biomass material with potassium bicarbonate, and heating in an inert atmosphere to prepare porous carbon powder; respectively drying the poly (vinylidene fluoride-co-hexafluoropropylene), the lithium salt, the additive and the solvent for later use;
s2: mixing the dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium salt and additive, adding the mixture into the solvent, and heating and stirring the mixture to obtain a mixed solution A; ultrasonically dispersing the porous carbon powder into the solvent to obtain a mixed solution B;
s3: mixing the mixed solution A and the mixed solution B, heating and stirring to fully disperse the mixed solution A and the mixed solution B to obtain precursor slurry;
s4: removing bubbles from the precursor slurry in a vacuum bubble removing machine until no bubbles are generated, so as to obtain bubble-free precursor slurry;
s5: and transferring the bubble-free precursor slurry into a mold, and drying to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
Preferably, the biomass material is cellulose, the lithium salt is lithium bistrifluoromethanesulfonylimide, the additive is lithium nitrate, and the solvent is N-methylpyrrolidone.
Preferably, the preparation method of the porous carbon powder is specifically as follows:
mixing the biomass material and potassium bicarbonate according to the mass ratio of 1:4, heating to 800 ℃ at the speed of 15 ℃/min in an inert atmosphere, then preserving the heat for 1 hour at 800 ℃, naturally cooling to room temperature, alternately ultrasonically washing with deionized water and ethanol, and drying to obtain the porous carbon powder.
Further, in the mixed solution a, the mixing mass ratio of the poly (vinylidene fluoride-co-hexafluoropropylene), the lithium salt and the additive is 6: 4: 1; the ratio of solvent to poly (vinylidene fluoride-co-hexafluoropropylene) was 9ml:1 g.
Further, in the mixed solution A, 1g of poly (vinylidene fluoride-co-hexafluoropropylene), 0.67g of lithium salt, 0.17g of an additive and 9ml of a solvent were added.
Preferably, in the mixed solution B, the mass of the porous carbon powder is 1wt% of the mass of the solvent.
Further, in the mixed solution B, 10mg of porous carbon powder and 1ml of solvent were used.
Preferably, the mass of the solvent in the precursor slurry is the same as the mass of the poly (vinylidene fluoride-co-hexafluoropropylene).
Preferably, in S2, adding the porous carbon powder into a solvent, and performing ultrasonic dispersion for 20min to obtain a mixed solution B; in the step S3, stirring the mixed solution A and the mixed solution B at the temperature of 60 ℃ for 12 hours at the rotating speed of 600 revolutions per minute to obtain precursor slurry; in the S5, the drying temperature is 60 ℃, and the drying time is 24 hours.
In another aspect, the invention provides a solvent and porous carbon reinforced composite polymer electrolyte obtained according to the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the solvent-reinforced porous carbon composite polymer electrolyte prepared by the solution pouring method has a porous carbon reinforced structure and solvated lithium ion carriers. The solvated lithium ions are used as carriers of the polymer electrolyte, and play a role of a plasticizer, so that the ionic conductivity of the polymer is greatly improved. However, higher concentrations of solvated lithium ions significantly degrade the mechanical properties of the polymer electrolyte. The combination of the porous carbon obviously enhances the mechanical strength and the processability of the polymer electrolyte under the condition of not losing the high ionic conductivity of the polymer electrolyte.
Drawings
FIG. 1 is a scanning electron microscope picture of a solvent and porous carbon reinforced composite polymer electrolyte prepared in example 1;
FIG. 2 is a plot of constant current cycling voltage versus time for a lithium electrode of the solvent and porous carbon reinforced composite polymer electrolyte prepared in example 2;
FIG. 3 is a plot of constant current cycling voltage versus time for a lithium electrode using a solvent and porous carbon reinforced composite polymer electrolyte prepared in examples 1 and 3;
FIG. 4 is a plot of constant current cycling voltage versus time for a lithium electrode using a solvent and porous carbon reinforced composite polymer electrolyte prepared in example 4.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
The invention provides a preparation method of a solvent and porous carbon reinforced composite polymer electrolyte, which comprises the following steps:
s1: firstly, mixing a biomass material and potassium bicarbonate according to a mass ratio of 1:4, heating to 800 ℃ at a speed of 15 ℃/min in an inert atmosphere, then preserving heat at 800 ℃ for 1 hour, naturally cooling to room temperature, alternately ultrasonically washing with deionized water and ethanol, and drying to obtain porous carbon powder.
Respectively drying the poly (vinylidene fluoride-co-hexafluoropropylene), the lithium salt, the additive and the solvent for later use.
In practical application, the biomass material can adopt cellulose, hemicellulose, starch or the like, and preferably adopts cellulose; the lithium salt can adopt lithium bistrifluoromethanesulfonimide, lithium bistrifluoromethanesulfonimide or lithium bisoxalato borate, and preferably adopts lithium bistrifluoromethanesulfonimide; the additive can adopt lithium nitrate, lithium fluoride or fluoroethylene carbonate, and preferably adopts lithium nitrate; the solvent may be N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide, and N-methylpyrrolidone is preferably used.
S2: drying poly (vinylidene fluoride-co-hexafluoropropylene), lithium salt and additive according to the mass ratio of 6: 4: 1, adding the mixture into a solvent, heating and stirring to obtain a mixed solution A. In the mixed solution A, the ratio of the solvent to poly (vinylidene fluoride-co-hexafluoropropylene) was 9ml:1 g.
And adding the obtained porous carbon powder into a solvent for ultrasonic dispersion for 20min to obtain a mixed solution B. In the mixed solution B, the mass of the porous carbon powder was 1wt% of the mass of poly (vinylidene fluoride-co-hexafluoropropylene).
Wherein, the additive is added in the preparation process mainly as follows: the matrix of the solvent and the porous carbon reinforced composite polymer electrolyte is poly (vinylidene fluoride-co-hexafluoropropylene), a vinylidene fluoride chain segment of the poly (vinylidene fluoride-co-hexafluoropropylene) undergoes dehydrofluorination reaction with a lithium electrode under high current to cause the performance of the composite polymer electrolyte to be rapidly attenuated, and the interface of the polymer and the lithium electrode can be stabilized by adding the additive lithium nitrate, so that the solvent and the porous carbon reinforced composite polymer electrolyte can also stably run under high current.
S3: and mixing the obtained mixed solution A and the mixed solution B, and stirring at the rotating speed of 600 revolutions per minute for 12 hours at the temperature of 60 ℃ to obtain precursor slurry. The mass of the solvent in the precursor slurry was the same as the mass of poly (vinylidene fluoride-co-hexafluoropropylene).
S4: and (4) defoaming the obtained precursor slurry in a vacuum defoaming machine for multiple times until no bubbles are generated, so as to obtain the bubble-free precursor slurry.
S5: and transferring the obtained bubble-free precursor slurry into a quartz mold, and drying at the temperature of 60 ℃ for 24 hours to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
Example 1
1) Mixing cellulose (biomass material) and potassium bicarbonate according to a ratio of 1:4, and are transferred together into a tube furnace. Heating in a tubular furnace under the protection of argon atmosphere, heating to 800 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour at 800 ℃, naturally cooling to room temperature after heat treatment, alternately ultrasonically washing three times by using deionized water and ethanol, then placing in a drying box, and drying for 12 hours at 60 ℃ to obtain the porous carbon powder.
1g of poly (vinylidene fluoride-co-hexafluoropropylene), 0.67g of lithium bistrifluoromethanesulfonimide and 0.17g of lithium nitrate were dried in a glove box at a temperature of 80 ℃ for 12 hours, and N-methylpyrrolidone was dried over a molecular sieve.
2) The dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium bistrifluoromethanesulfonylimide and lithium nitrate were transferred to a flask, 9ml of dried N-methylpyrrolidone was added, and the mixture was stirred at 60 ℃ at a rotation speed of 600 rpm for 12 hours to obtain a mixed solution a.
The obtained 10mg of porous carbon powder was dispersed in 1ml of N-methylpyrrolidone by ultrasonic dispersion to obtain a mixed solution B.
3) And mixing the obtained mixed solution A and the mixed solution B, and stirring at the rotating speed of 600 revolutions per minute for 12 hours at the temperature of 60 ℃ to obtain precursor slurry.
4) And (4) defoaming the obtained precursor slurry in a vacuum defoaming machine for multiple times until no bubbles are generated, so as to obtain the bubble-free precursor slurry.
5) And finally, transferring the obtained bubble-free precursor slurry into a quartz mold, and drying at the temperature of 60 ℃ for 24 hours to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
A scanning electron microscope picture of the solvent and porous carbon reinforced composite polymer electrolyte prepared in this embodiment is shown in fig. 1, wherein the left picture is a sectional view of the electrolyte, and the right picture is a surface view of the electrolyte.
The electrolyte membrane was punched out into a 16mm diameter green sheet by a microtome. And packaging the cut solvent, the porous carbon reinforced composite polymer electrolyte and the lithium electrode in the CR2032 battery by using a hydraulic button battery sealing machine. The packaged battery was subjected to lithium stripping/deposition cycling test on a battery test system to obtain a voltage-time curve (FIG. 3) with a constant current cycling of 0.2mA cm-2And charging for 1 hour and discharging for 1 hour in a single cycle.
From fig. 3, the effect of solvent plasticization and solvation on cycle stability at a suitable lithium salt content and drying temperature can be seen visually, and under the conditions of example 1, the lithium battery can be stably cycled for 1000 hours.
Example 2
1) Mixing cellulose (biomass material) and potassium bicarbonate according to a ratio of 1:4, and are transferred together into a tube furnace. Heating in a tubular furnace under the protection of argon atmosphere, heating to 800 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour at 800 ℃, naturally cooling to room temperature after heat treatment, alternately ultrasonically washing three times by using deionized water and ethanol, then placing in a drying box, and drying for 12 hours at 60 ℃ to obtain the porous carbon powder.
1g of poly (vinylidene fluoride-co-hexafluoropropylene), 1g of lithium bistrifluoromethanesulfonimide and 0.25g of lithium nitrate were dried in a glove box at 80 ℃ for 12 hours and the N-methylpyrrolidone was dried over molecular sieves.
2) The dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium bistrifluoromethanesulfonylimide and lithium nitrate were transferred to a flask, 9ml of dried N-methylpyrrolidone was added, and the mixture was stirred at 60 ℃ at a rotation speed of 600 rpm for 12 hours to obtain a mixed solution a.
The obtained 10mg of porous carbon powder was dispersed in 1ml of N-methylpyrrolidone by ultrasonic dispersion to obtain a mixed solution B.
3) And mixing the obtained mixed solution A and the mixed solution B, and stirring at the rotating speed of 600 revolutions per minute for 12 hours at the temperature of 60 ℃ to obtain precursor slurry.
4) And (4) defoaming the obtained precursor slurry in a vacuum defoaming machine for multiple times until no bubbles are generated, so as to obtain the bubble-free precursor slurry.
5) And finally, transferring the obtained bubble-free precursor slurry into a quartz mold, and drying at the temperature of 100 ℃ for 24 hours to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
The basic structure of the solvent and porous carbon reinforced composite polymer electrolyte obtained in this example is similar to that of example 1. However, since the content of lithium bistrifluoromethanesulfonylimide in the preparation of this example is increased and the drying temperature in step 5) is increased to 100 ℃, the solvent and porous carbon reinforced composite polymer electrolyte prepared in this example is only the solvent and porous carbon reinforced composite polymer electrolyte obtained by the component adjustment in example 1.
As shown in fig. 2, increasing the content of lithium salt while increasing the drying temperature has an effect on the plasticization and solvation of the solvent on the cycle stability. Under the conditions of example 2, the lithium battery can be stably cycled for 600 hours, and the lithium battery still has good stable cycling performance although the stable cycling time is shorter than that of example 1.
Therefore, the preparation system of the present invention requires matching of the lithium salt content with the drying temperature to meet the performance requirements of the environment in which it is used. To further verify this conclusion, the influence of the relationship between the lithium salt content and the drying temperature on the performance of the finally prepared solvent and porous carbon reinforced composite polymer electrolyte will be illustrated by examples 3 and 4 below.
Example 3
1) Mixing cellulose (biomass material) and potassium bicarbonate according to a ratio of 1:4, and are transferred together into a tube furnace. Heating in a tubular furnace under the protection of argon atmosphere, heating to 800 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour at 800 ℃, naturally cooling to room temperature after heat treatment, alternately ultrasonically washing three times by using deionized water and ethanol, then placing in a drying box, and drying for 12 hours at 60 ℃ to obtain the porous carbon powder.
1g of poly (vinylidene fluoride-co-hexafluoropropylene), 0.67g of lithium bistrifluoromethanesulfonimide and 0.17g of lithium were dried in a glove box at 80 ℃ for 12 hours and the N-methylpyrrolidone was dried over molecular sieves.
2) The dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium bistrifluoromethanesulfonylimide and lithium nitrate were transferred to a flask, 9ml of dried N-methylpyrrolidone was added, and the mixture was stirred at 60 ℃ at a rotation speed of 600 rpm for 12 hours to obtain a mixed solution a.
The obtained 10mg of porous carbon powder was dispersed in 1ml of N-methylpyrrolidone by ultrasonic dispersion to obtain a mixed solution B.
3) And mixing the obtained mixed solution A and the mixed solution B, and stirring at the rotating speed of 600 revolutions per minute for 12 hours at the temperature of 60 ℃ to obtain precursor slurry.
4) And (4) defoaming the obtained precursor slurry in a vacuum defoaming machine for multiple times until no bubbles are generated, so as to obtain the bubble-free precursor slurry.
5) And finally, transferring the obtained bubble-free precursor slurry into a quartz mold, and drying at the temperature of 100 ℃ for 24 hours to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
The constant current cycle test of the solvent and porous carbon reinforced composite polymer electrolyte prepared in the embodiment on lithium is shown in fig. 3. Example 3 compared to example 1, increasing the drying temperature without changing the lithium salt content did not allow stable cycling of the solvent with the porous carbon reinforced composite polymer electrolyte.
Example 4
1) Mixing cellulose (biomass material) and potassium bicarbonate according to a ratio of 1:4, and are transferred together into a tube furnace. Heating in a tubular furnace under the protection of argon atmosphere, heating to 800 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour at 800 ℃, naturally cooling to room temperature after heat treatment, alternately ultrasonically washing three times by using deionized water and ethanol, then placing in a drying box, and drying for 12 hours at 60 ℃ to obtain the porous carbon powder.
1g of poly (vinylidene fluoride-co-hexafluoropropylene), 0.33g of lithium bistrifluoromethanesulfonimide and 0.08 g of lithium nitrate were dried in a glove box at a temperature of 80 ℃ for 12 hours, and N-methylpyrrolidone was dried over molecular sieves.
2) The dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium bistrifluoromethanesulfonylimide and lithium nitrate were transferred to a flask, 9ml of dried N-methylpyrrolidone was added, and the mixture was stirred at 60 ℃ at a rotation speed of 600 rpm for 12 hours to obtain a mixed solution a.
The obtained 10mg of porous carbon powder was dispersed in 1ml of N-methylpyrrolidone by ultrasonic dispersion to obtain a mixed solution B.
3) And mixing the obtained mixed solution A and the mixed solution B, and stirring at the rotating speed of 600 revolutions per minute for 12 hours at the temperature of 60 ℃ to obtain precursor slurry.
4) And (4) defoaming the obtained precursor slurry in a vacuum defoaming machine for multiple times until no bubbles are generated, so as to obtain the bubble-free precursor slurry.
5) And finally, transferring the obtained bubble-free precursor slurry into a quartz mold, and drying at the temperature of 60 ℃ for 24 hours to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
The lithium constant current cycle test of the solvent and the porous carbon reinforced composite polymer electrolyte prepared in the embodiment is shown in fig. 4. Example 4 compared to example 1, the decrease in the lithium salt content did not allow stable cycling of the solvent with the porous carbon-reinforced composite polymer electrolyte without changing the drying temperature.
The solvent-reinforced porous carbon composite polymer electrolyte prepared by the solution pouring method has a porous carbon reinforced structure and solvated lithium ion carriers. The solvated lithium ions are used as carriers of the polymer electrolyte, and play a role of a plasticizer, so that the ionic conductivity of the polymer is greatly improved. However, higher concentrations of solvated lithium ions significantly degrade the mechanical properties of the polymer electrolyte. The combination of the porous carbon obviously enhances the mechanical strength and the processability of the polymer electrolyte under the condition of not losing the high ionic conductivity of the polymer electrolyte.
In addition, in the present invention, the specific parameters and materials of each step can be reasonably adjusted according to the needs. For example, the lithium salt used may be other lithium salts, but it is desirable to have a larger anion volume and a better dissociation degree in order to act as a plasticizer to reduce the crystallinity of the polymer and to increase the ionic conductivity, such as bis (oxalato) borate, bis (perfluoroethanesulfonyl) imide, and the like. In addition, the types and the addition amounts of the additives can be adjusted, so that the battery pack is suitable for different battery systems.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (11)
1. A preparation method of a solvent and porous carbon reinforced composite polymer electrolyte is characterized by comprising the following steps:
s1: mixing the biomass material with potassium bicarbonate, and heating in an inert atmosphere to prepare porous carbon powder;
s2: mixing dried poly (vinylidene fluoride-co-hexafluoropropylene), lithium salt and additive, adding into a solvent, heating and stirring to obtain a mixed solution A; then ultrasonically dispersing the porous carbon powder into the solvent to obtain a mixed solution B;
s3: mixing the mixed solution A and the mixed solution B, heating the mixed solution A and the mixed solution B, and fully dispersing the mixed solution A and the mixed solution B to obtain precursor slurry;
s4: removing bubbles from the precursor slurry until no bubbles are generated, and obtaining bubble-free precursor slurry;
s5: and transferring the bubble-free precursor slurry into a mold, and drying to obtain the solvent and porous carbon reinforced composite polymer electrolyte.
2. The method according to claim 1, wherein the biomass material is cellulose, the lithium salt is lithium bistrifluoromethanesulfonylimide, the additive is lithium nitrate, and the solvent is N-methylpyrrolidone.
3. The method according to claim 1 or 2, wherein the porous carbon powder is prepared by a specific method as follows:
mixing the biomass material and potassium bicarbonate according to the mass ratio of 1:4, heating to 800 ℃ at the speed of 15 ℃/min in an inert atmosphere, then preserving the heat for 1 hour at 800 ℃, naturally cooling to room temperature, alternately ultrasonically washing with deionized water and ethanol, and drying to obtain the porous carbon powder.
4. The production method according to claim 3, wherein the mixing mass ratio of the poly (vinylidene fluoride-co-hexafluoropropylene), the lithium salt, and the additive in the mixed solution A is 6: 4: 1; the ratio of solvent to poly (vinylidene fluoride-co-hexafluoropropylene) was 9ml:1 g.
5. The production method according to claim 4, wherein the mixed solution A contains 1g of poly (vinylidene fluoride-co-hexafluoropropylene), 0.67g of lithium salt, 0.17g of additive, and 9ml of solvent.
6. The production method according to claim 4 or 5, characterized in that the mass of the porous carbon powder in the mixed solution B is 1wt% of the mass of the poly (vinylidene fluoride-co-hexafluoropropylene).
7. The production method according to claim 6, wherein the mixed solution B contains 10mg of the porous carbon powder and 1ml of the solvent.
8. The method according to claim 6, wherein the mass of the solvent in the precursor slurry is the same as the mass of poly (vinylidene fluoride-co-hexafluoropropylene).
9. The method according to claim 7, wherein the mass of the solvent in the precursor slurry is the same as the mass of poly (vinylidene fluoride-co-hexafluoropropylene).
10. The preparation method according to claim 1, wherein in S2, the porous carbon powder is added to a solvent and ultrasonically dispersed for 20min to obtain a mixed solution B; in the step S3, stirring the mixed solution A and the mixed solution B at the temperature of 60 ℃ for 12 hours at the rotating speed of 600 revolutions per minute to obtain precursor slurry; in the S5, the drying temperature is 60 ℃, and the drying time is 24 hours.
11. The solvent and porous carbon reinforced composite polymer electrolyte obtained by the preparation method according to any one of claims 1 to 10.
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