All-solid-state electrolyte membrane of fluorine-containing filler and preparation method of all-solid-state electrolyte membrane

Abstract

The invention discloses an all-solid-state electrolyte membrane of a fluorine-containing filler and a preparation method of the all-solid-state electrolyte membrane, and belongs to the field of energy storage technology application, the high-performance fluorine-containing all-solid-state electrolyte membrane is produced and prepared by organically combining an electrolyte and graphdiyne fluoride, performing parameter configuration and process optimization, and performing slurry mixing, spin coating and other means. The function of effectively regulating and controlling ion migration in the solid electrolyte by using a two-dimensional carbon fluoride-based material as a filler is realized, the fluorinated graphdiyne filler is introduced into the solid electrolyte, and the high specific surface area and active sites of the graphdiyne filler can promote close contact between an electrode and the electrolyte, so that the charge transfer efficiency is improved, the interface phase fusion problem is reduced, and the interface resistance is reduced; the overall performance of the battery is improved.

Description

Technical Field

[0001] The present invention relates to the application field of energy storage technology, and in particular to an all-solid-state electrolyte membrane containing fluorine filler and a preparation method thereof. Background Art

[0002] As a key material in the battery field, the performance of all-solid-state electrolytes directly impacts important battery performance indicators such as energy density, safety, and cycle life. The development of high-performance all-solid-state electrolytes can effectively improve battery energy density and provide longer-lasting battery life, while effectively avoiding the safety hazards associated with traditional liquid electrolyte batteries caused by electrolyte leakage. These developments provide critical support for the development of electric vehicles, large-scale energy storage, and other fields, and have become a research hotspot and key challenge in the battery field. Compared to inorganic solid electrolytes, all-solid polymer electrolytes (ASPEs) exhibit excellent flexibility and processability and are considered one of the most promising all-solid-state electrolytes. However, their relatively low ionic conductivity and low lithium-ion transference number (LTN) still present several deficiencies in practical applications. For example, the difficulty in achieving ideal ionic conductivity at room temperature limits the battery's charge and discharge performance, while the low LTN affects the battery's rate capability and cycling stability. The low ionic conductivity and high interfacial impedance of ASPEs stem from their high crystallinity, restricted segmental motion, and insufficient lithium salt dissociation, while the low LTN is due to the free migration of anions and ion association effects. By adding fillers to interact with the various ASPE components, the amorphous region can be effectively increased, the matrix crystallinity can be reduced, and the ionic conductivity can be improved. At the same time, the interaction between the filler and the lithium salt can be improved, which promotes dissociation and increases the ion mobility. The existing ASPE fillers mainly include inorganic oxide fillers, organic-inorganic hybrid fillers, ceramic fillers and fluoropolymer fillers. Among them, inorganic oxide fillers, organic-inorganic hybrid fillers and ceramic fillers all rely on oxygen-containing groups (such as -OH, -COOH), oxygen / sulfur ions (O 2- 、S 2- ), oxygen vacancies, amino groups (-NH2) or Lewis acid sites, etc., which destroy the crystalline structure of the polymer matrix (such as PEO), inhibit polymer crystallization, increase amorphous areas, promote chain segment movement, or react with Li + The overall performance of the ASPE system is improved by promoting interaction, promoting lithium salt dissociation, optimizing ion transmission paths, etc. Compared with other fillers, fluorine-containing fillers have better advantages at the molecular level, microstructure, and interface dimensions. The high electronegativity of the CF bond (electronegativity 4.0) precisely regulates ion dissociation and migration through the inductive effect, greatly increasing the free Li + concentration; steric hindrance effect (bond length) of fluorinated functional groups (such as -CF2-) The bond angle is 109.5°), which can effectively reduce the crystallization of the ASPE matrix and maintain a highly amorphous phase; the CF bond and the Li metal in situ generate a thin and dense LiF layer (thickness <50nm), which simultaneously reduces the impedance and dendrite risk. These advantages make fluorinated fillers the only ones with high conductivity (>10 -4 ASPE fillers that meet the standards for three indicators at the same time: high S / cm), migration number (>0.6) and interface stability (cycle>1000h) have become an important research direction for optimizing the comprehensive performance of ASPE and developing high-energy-density lithium metal batteries.

[0003] Fluorine is not a "panacea" but a "scalpel" that requires precise positioning. The current problem facing fluorine-containing polymer fillers is essentially an over-reliance on the single advantage of fluorine (such as high stability) while ignoring its systematic defects. It is necessary to turn to "functional targeted fluorination" and develop new methods for qualitatively and quantitatively introducing fluorine at specific sites, as well as combining the synergistic effect of the ASPE system matrix and lithium salts to maintain the advantages of fluorine while circumventing its limitations. Moderate fluorination will help the development of long-cycle all-solid-state batteries. Precisely controlling the physicochemical properties, electronic structure, synergistic interactions and multi-scale structure of the filler can synergistically optimize its ion transport, mechanical strength and interface stability, breaking through the performance bottleneck of traditional ASPE. Precisely introducing heteroatoms (such as F) on the surface of the filler, increasing the uniformly distributed CF bonds to regulate the electron distribution of two-dimensional materials (such as graphyne), and developing fluorine-containing fillers with ordered potential regions (such as alternating structures of electron-rich and electron-poor regions) can effectively enhance the coordination effect with lithium ions, promote lithium ion migration and inhibit anion migration. However, the precise design and controllable preparation of nanofillers, their structural impact on the ion conduction mechanism of ASPE, and their interfacial compatibility with electrode materials remain unresolved, limiting the further development of ASPE. Therefore, combining materials genomics with advanced manufacturing technologies to optimize the structural design and controllable preparation of nanofillers, and to explore their mechanism of action in ASPE, are urgent scientific issues to promote the development of all-solid-state batteries. Summary of the Invention

[0004] The purpose of the present invention is to provide an all-solid-state electrolyte membrane containing fluorine filler and a preparation method thereof. By organically combining the electrolyte and fluorinated graphene, through parameter configuration and process optimization, and through slurry mixing, spin coating and other means, a high-performance fluorine-containing all-solid-state electrolyte membrane is produced and prepared, realizing the function of two-dimensional fluorinated carbon-based materials as fillers to effectively regulate ion migration in solid electrolytes.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0007] Step 1: Trifluorotriiodobenzene, cuprous iodide and bis(triphenylphosphine)palladium dichloride are added to a stirring tank of a slurry mixer. After three argon replacements, a 2-4% mass fraction of triethylamine solution is added, and the mixture is stirred at 20-25° C. and 500-600 r / min for 40-60 minutes. Then, 1,3,5-trifluorobenzene after deprotection, extraction and rotary evaporation is added, and the mixture is further stirred to dissolve. The mixture is heated to 60-70° C. and stirred for 72-74 hours. The mixture is filtered, and the precipitate is washed 2-3 times with a 1% hydrochloric acid solution and deionized water, respectively, and dried in vacuo at 60-80° C. for 1-2 hours to obtain fluorinated graphene powder.

[0008] Step 2: Add polyvinylidene fluoride-hexafluoropropylene copolymer and N-methylpyrrolidone as electrolyte powder into the stirring tank of the mixer, stir at 20-25°C and 500-600r / min for 12-14h, then add fluorinated graphene powder, ultrasonically disperse for 4-5h, continue stirring and mixing for 24-26h, then add lithium bis(trifluoromethylsulfonyl)imide, heat to 90-100°C, continue stirring for 12-14h to form a uniform slurry, and evenly coat the slurry on a glass plate by spin coating. After spin coating for 30-40s, annealing is performed for 30-40min, and the annealing time is transferred to a vacuum oven and dried at 80-90°C for 24-26h to obtain an all-solid-state electrolyte membrane containing fluorine filler.

[0009] Preferably, in step 1, the usage ratio of trifluorotriiodobenzene, cuprous iodide, bis(triphenylphosphine)palladium dichloride, triethylamine solution and 1,3,5-trifluorobenzene is 80-90 g: 4-5 g: 2-3 g: 300-400 mL: 50-60 mL.

[0010] Preferably, the mass of the fluorinated graphene accounts for 1.5-5% of the total mass of the slurry.

[0011] Preferably, the total mass of the polyvinylidene fluoride-hexafluoropropylene copolymer and lithium bis(trifluoromethylsulfonyl)imide accounts for 95-98.5% of the non-volatile matter.

[0012] Preferably, the electrolyte powder is any one of PVDF-HFP, PVDF, PEO, PPC, and PMMA, and the proportion of the total mass of the electrolyte powder in the non-volatile matter is 45-52%.

[0013] Preferably, the solid content of the slurry is 21-30%, and the viscosity of the slurry is in the range of 3000-6000 mPa.s.

[0014] Preferably, the rotation speed of the spin coating is 300-600 r / min, and the acceleration is controlled at 800-1200 rpm / s.

[0015] Preferably, the annealing time is 20-40 min.

[0016] Preferably, the thickness of the all-solid electrolyte membrane is 50-150 μm.

[0017] The present invention also provides an all-solid electrolyte membrane containing fluorine filler, which is prepared by the above-mentioned method.

[0018] Beneficial effects of the present invention:

[0019] 1. Improve ion conductivity and transmission efficiency. The two-dimensional porous structure of graphyne is realized by sp and sp 2 The π-conjugated network formed by hybridization has uniformly distributed pores, which can selectively transmit lithium ions and block anions, thereby optimizing the ion transmission path. Fluorination treatment may further enhance its surface chemical properties, increase ion mobility, and enhance kinetic performance. At the same time, its high conductivity can reduce interface resistance and enhance the rate performance of the overall battery.

[0020] 2. Inhibit the growth of lithium dendrites. In interface engineering, the three-dimensional network structure formed by fluorinated graphene can stabilize the interface between the electrode and the electrolyte, preventing short-circuit problems caused by lithium dendrite penetration. Fluorinated graphene further enhances the protection of the lithium metal negative electrode through stronger chemical bonding, has a high affinity for lithium, and its uneven surface charge distribution can homogenize the lithium ion flow, reduce local charge aggregation, and improve the overall safety performance of the battery. The fluorine-containing filler is fluorinated graphene, which has a clear fluorine doping site and fluorine content. It can be used as a solid electrolyte membrane filler to improve the overall performance of the device, promote the dissociation of LiTFSI, and accelerate the migration of lithium ions, reduce the crystallinity of the solid electrolyte, and make the electrolyte membrane have better interface compatibility. In addition, the formation of a solid electrolyte interface uniformly rich in LiF can effectively inhibit the growth of lithium dendrites, thereby ensuring excellent interface stability.

[0021] 3. Optimize the interfacial compatibility between the electrolyte and the electrode. After the fluorinated graphene filler is introduced into the solid electrolyte, its high specific surface area and active sites can promote close contact between the electrode and the electrolyte, improve the charge transfer efficiency, reduce the interfacial fusion problem, reduce the interfacial resistance, and improve the overall performance of the battery.

[0022] 4. Improve battery safety and thermal stability. The inherent non-flammability of all-solid-state electrolytes has significantly enhanced battery safety, and the introduction of fluorinated graphene may further suppress the risk of thermal runaway through its high thermal stability and chemical inertness. The natural band gap and semiconducting properties of graphyne help regulate the battery's photoelectric response, indirectly enhancing system safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The molecular skeleton of the fluorinated graphene prepared by the present invention;

[0024] Figure 2 This is a scanning electron microscope image of the fluorinated graphene prepared in Example 1 of the present invention;

[0025] Figure 3 This is the Raman spectrum of the fluorinated graphene prepared in Example 1 of the present invention;

[0026] Figure 4 This is the infrared spectrum of the fluorinated graphene prepared in Example 1 of the present invention;

[0027] Figure 5 This is the solid-state NMR spectrum of fluorinated graphene prepared in Example 1 of the present invention;

[0028] Figure 6 This is the X-ray diffraction spectrum of the fluorinated graphene prepared in Example 1 of the present invention;

[0029] Figure 7 This is a physical picture of the fluorinated graphene-based solid electrolyte membrane prepared in Example 1 of the present invention;

[0030] Figure 8 The application performance of the fluorinated graphene-based solid electrolyte membrane prepared in Example 1 of the present invention in a battery;

[0031] Figure 9 This is the application performance of the fluorinated graphene-based solid electrolyte membrane prepared in Example 1 of the present invention in an all-solid-state battery. DETAILED DESCRIPTION

[0032] The following examples further describe in detail an all-solid-state electrolyte fluorine-containing filler and a preparation method thereof described in the present invention. For the sake of simplicity of description, this document cannot enumerate all the alternative technical features and implementation schemes contained in the present invention. Therefore, those skilled in the art should know that any technical features and implementation schemes in this embodiment do not limit the scope of protection of the present invention, which includes any alternative technical features and implementation schemes adopted by all those skilled in the art without creative work. Specifically, the implementation schemes obtained by replacing any technical feature in the present invention or combining any two or more technical features provided by the present invention should be within the scope of protection of the present invention.

[0033] Example 1

[0034] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0035] S1: 80 g of trifluorotriiodobenzene, 4 g of cuprous iodide, and 2 g of bis(triphenylphosphine)palladium dichloride were added to a reactor. After three argon replacements, 300 mL of 2% triethylamine solution was added and stirred at 20°C and 500 r / min for 40 min. Then, 50 mL of 1,3,5-trifluorobenzene that had been deprotected, extracted, and rotary evaporated was added. After continued stirring to dissolve, the mixture was heated to 60°C and stirred for 72 h. The mixture was filtered and the precipitate was washed twice with 1% hydrochloric acid solution and deionized water, respectively, and dried in vacuo at 60°C for 1 h to obtain fluorinated graphene powder.

[0036] S2: Add polyvinylidene fluoride-hexafluoropropylene copolymer and N-methylpyrrolidone as electrolyte powder into the stirring tank of the mixer, stir at 20°C and 500r / min for 12h, then add fluorinated graphene powder, ultrasonically disperse for 4h, continue stirring and mixing for 24h, then add lithium bis(trifluoromethylsulfonylimide), heat to 90°C, continue stirring for 12h to form a uniform slurry, and evenly coat the slurry on a glass plate by spin coating at a speed of 500r / min and an acceleration of 1000rpm / s. After rotating at the above speed and acceleration for 30s, annealing is performed for 30min, and the mixture is transferred to a vacuum oven and dried at 80°C for 24h to obtain a fluorine-containing filler-containing all-solid-state electrolyte membrane with a thickness of 50μm.

[0037] The scanning electron microscopy image of the prepared fluorinated graphene is shown in Figure 2. Figure 2 As shown, fluorine doping further enables the structure to have a larger surface area and higher porosity, providing abundant ion transport channels and active sites for lithium storage.

[0038] The Raman spectrum of the prepared fluorine-containing graphyne is as follows Figure 3 As shown, at 2132.70cm -1 The obvious peak at 1939.96 cm represents the stretching vibration of butadiene, which is consistent with the peak at 1939.96 cm -1 The Raman peak is consistent with 1557.61cm -1 The peak at 1354.48 cm indicates sufficient benzene rings, while the peak at 1354.48 cm -1 Peaks indicate edges.

[0039] The infrared spectrum of the prepared fluorinated graphene is as follows Figure 4 As shown, at 2208.46cm -1 The peak at represents C ≡ C stretching vibration, at 1620.00cm -1 and 1453.85cm -1 The obvious peak at 1128.46 cm indicates C=C or benzene ring skeleton. -1 and 1052.31cm -1 represents the vibration of the CF bond.

[0040] The solid-state NMR spectrum of the prepared fluorine-containing graphyne is as follows: Figure 5 As shown, 99.32ppm in the CF spectrum is the fluorine atom and sp 3 C forms a covalent bond, indicating the existence of a highly fluorinated graphyne structure, and the C-F bond environment is single, with no other C signals coupled to F. The 162.83 ppm peak is sp 2 The hybridized CF bonds or partially fluorinated benzene ring carbons may be incomplete fluorination areas, while the 225.49 ppm position may be the carbonyl carbon produced by oxidation upon exposure to air.

[0041] The X-ray diffraction spectrum of the prepared fluorinated graphene is shown in Figure 6 As shown in the figure, the doping of fluorine atoms leads to an increase in the interlayer spacing, which causes the surface diffraction peak of graphyne to move to a lower angle, and the broadened bun peak indicates a lower crystallinity and enhanced amorphous characteristics.

[0042] The charge-discharge cycle diagram of the button cell assembled with the prepared fluorine-containing all-solid-state electrolyte membrane at a current density of 1C is shown in the figure. After 350 cycles, the gram capacity of the active material is about 180 mAh / g, and the average charge-discharge efficiency is 99.1%.

[0043] Example 2

[0044] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0045] The mass ratio of electrolyte to graphyne used was 9.5:0.5, the total mass accounted for 4.8% of the non-volatile matter of the solid electrolyte membrane, the total mass of the binder PVDF-HFP used accounted for 47.6% of the non-volatile matter of the solid electrolyte membrane, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane was 47.6%, and the amount of NMP was calculated based on a solid content of 23.5%.

[0046] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0047] Example 3

[0048] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0049] The mass ratio of electrolyte to graphyne used was 9:1, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane was 9.6%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane was 45.2%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane was 45.2%, and the amount of NMP was calculated based on a solid content of 23.5%.

[0050] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0051] Example 4

[0052] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0053] The mass ratio of electrolyte to graphyne used is 8.1:1.9, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 19.2%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 40.4%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 40.4%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0054] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0055] Example 5

[0056] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0057] The mass ratio of electrolyte to graphyne used is 6.2:3.8, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 38.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 30.8%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 30.8%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0058] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0059] Example 6

[0060] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0061] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 48.8%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 48.8%, and the amount of NMP is calculated based on a solid content of 21%.

[0062] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0063] Example 7

[0064] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0065] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 48.8%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 48.8%, and the amount of NMP is calculated based on a solid content of 25%.

[0066] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0067] Example 8

[0068] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0069] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 48.8%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 48.8%, and the amount of NMP is calculated based on a solid content of 28%.

[0070] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0071] Example 9

[0072] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0073] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 61%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 36.6%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0074] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0075] Example 10

[0076] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0077] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 73.2%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 24.4%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0078] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0079] Example 11

[0080] A method for preparing an all-solid-state electrolyte membrane containing fluorine filler comprises the following steps:

[0081] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 36.6%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 61%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0082] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0083] Example 12 A method for preparing an all-solid-state electrolyte membrane containing a fluorine-containing filler comprises the following steps:

[0084] The mass ratio of electrolyte to graphyne used is 9.8:0.2, the proportion of the total mass in the non-volatile matter of the solid electrolyte membrane is 2.4%, the proportion of the total mass of the binder PVDF-HFP used in the non-volatile matter of the solid electrolyte membrane is 24.4%, the proportion of lithium bistrifluoromethylsulfonyl imide LiTFSI in the non-volatile matter of the solid electrolyte membrane is 73.2%, and the amount of NMP is calculated based on a solid content of 23.5%.

[0085] After determining the dosage of various substances, the subsequent steps were carried out with reference to Example 1.

[0086] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any simple modification, equivalent transformation and modification within the technical solution and principle of the present invention shall still fall within the scope of protection of the present invention.

Claims

1. A method for preparing an all-solid electrolyte membrane containing fluorine filler, characterized in that: The steps include: Step 1: Trifluorotriiodobenzene, cuprous iodide and bis(triphenylphosphine)palladium dichloride are added to a reaction kettle, and after three argon replacements, a 2-4 wt% triethylamine solution is added, and the mixture is stirred at 20-25° C. and 500-600 r / min for 40-60 min. Then, 1,3,5-trifluorobenzene that has been deprotected, extracted and rotary evaporated is added, and the mixture is stirred and dissolved. The mixture is heated to 60-70° C. and stirred for 72-74 h. The mixture is filtered and the precipitate is washed 2-3 times with a 1% hydrochloric acid solution and deionized water, respectively, and dried in vacuo to obtain fluorinated graphene powder. Step 2: Add polyvinylidene fluoride-hexafluoropropylene copolymer and N-methylpyrrolidone as electrolyte powder into the stirring tank of the slurry mixer, stir at 20-25°C and 500-600r / min for 12-14h, then add fluorinated graphene powder, ultrasonically disperse for 4-5h, continue stirring and mixing for 24-26h, then add lithium bis(trifluoromethylsulfonyl)imide, heat to 90-100°C, continue stirring for 12-14h to form a uniform slurry, and evenly coat the slurry on a glass plate by spin coating. After spin coating for 30-40s, annealing is performed for 30-40min, and the annealing time is transferred to a vacuum oven and dried at 80-90°C for 24-26h to obtain an all-solid-state electrolyte membrane containing fluorine filler.

2. The method for preparing a fluorine-containing filler all-solid-state electrolyte membrane according to claim 1, characterized in that: In step 1, the usage ratio of trifluorotriiodobenzene, cuprous iodide, bis(triphenylphosphine)palladium dichloride, triethylamine solution and 1,3,5-trifluorobenzene is 80-90 g: 4-5 g: 2-3 g: 300-400 mL: 50-60 mL.

3. The method for preparing a fluorine-containing filler all-solid-state electrolyte membrane according to claim 1, characterized in that: The mass of the fluorinated graphene accounts for 1.5-5% of the total mass of the slurry.

4. The method for preparing a fluorine-containing filler all-solid-state electrolyte membrane according to claim 1, characterized in that: The ratio of the total mass of the polyvinylidene fluoride-hexafluoropropylene copolymer and lithium bis(trifluoromethylsulfonyl)imide in the non-volatile matter is 95-98.5%.

5. The method for preparing a fluorine-containing filler all-solid electrolyte membrane according to claim 1, characterized in that: The electrolyte powder is any one of PVDF-HFP, PVDF, PEO, PPC or PMMA, and the proportion of the total mass of the electrolyte powder in the non-volatile matter is 45-52%.

6. The method for preparing a fluorine-containing filler all-solid-state electrolyte membrane according to claim 1, characterized in that: The solid content of the slurry is 21-30%, and the viscosity of the slurry is in the range of 3000-6000 mPa.s.

7. The method for preparing a fluorine-containing filler all-solid-state electrolyte membrane according to claim 1, characterized in that: The spin coating speed is 300-600 r / min, and the acceleration is controlled at 800-1200 rpm / s.

8. The method for preparing a fluorine-containing filler all-solid electrolyte membrane according to claim 1, characterized in that: The annealing time is 20-40 minutes.

9. The method for preparing a fluorine-containing filler all-solid electrolyte membrane according to claim 1, characterized in that: The thickness of the all-solid-state electrolyte membrane is 50-150 μm.

10. An all-solid electrolyte membrane containing fluorine filler, characterized in that: The method according to any one of claims 1 to 9 is used to prepare the present invention.

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