All-solid-state electrolyte and preparation method and application thereof

Abstract

The invention discloses an all-solid-state electrolyte and a preparation method and application thereof, and the preparation method of the all-solid-state electrolyte comprises the following steps: soaking a porous resin workpiece in a Li ion solid-state electrolyte solution, and obtaining the all-solid-state electrolyte after the solvent is completely volatilized. According to the invention, a Li-ion solid electrolyte solution (the Li-ion solid electrolyte solution is immersed into the pores of the porous resin in the form of a solution, and then is deposited and filled in the pores of the porous resin in the form of a volatile solvent) is introduced into the pore structure of the all-solid-state electrolyte; the porous resin is converted into a solid structure of the porous resin-all-solid-state electrolyte, so that the overall mechanical property of the material is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrolytes, and in particular relates to an all-solid-state electrolyte and a preparation method and application thereof. Background Art

[0002] Conventional energy storage materials, such as structural energy storage composites and button batteries using porous resin membranes as separators, can only use liquid electrolytes as the transmission medium, which severely limits the range of electrolyte options and their various functions. Specifically, structural energy storage composites prepared using porous resins and liquid electrolytes face the problem of overall mechanical performance deviations caused by the void structure. Summary of the Invention

[0003] In order to solve the above technical problems, one of the objectives of the present invention is to provide a method for preparing an all-solid-state electrolyte that is simple to prepare and has excellent performance.

[0004] In order to achieve the above object, the technical solution of the present invention is as follows: a method for preparing an all-solid-state electrolyte, wherein a porous resin part is immersed in a Li ion solid electrolyte solution, and the all-solid-state electrolyte is obtained after the solvent evaporates.

[0005] The method for preparing the porous resin article in the above technical solution comprises the following steps:

[0006] Step 1a: mixing the resin matrix and the pore-forming agent to form a uniform mixed solution;

[0007] Step 2a: adding a curing agent to the mixed solution 1, mixing to obtain a mixed solution 2, and molding the mixed solution 2 to obtain a green body;

[0008] Step 3a: Soak the green body in deionized water, then take it out and dry it to obtain a porous resin part.

[0009] The porous resin article described in the above technical solution must meet at least one of the following conditions during preparation:

[0010] A1: In step 1a, the mass ratio of the resin matrix to the pore-forming agent is 1:1-4 (it can be any ratio of 1:1, 1:2, 1:3, 1:4, or a range corresponding to any two ratios);

[0011] B1: In step 1a, the temperature for mixing the resin matrix and the pore-forming agent is 25-60° C. (can be any value among 25° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., and 60° C., or a range corresponding to any two values), and the stirring time is 0.2-0.5 h (can be any value among 0.2 h, 0.25 h, 0.3 h, 0.35 h, 0.4 h, 0.45 h, and 0.5 h, or a range corresponding to any two values);

[0012] C1: The mass ratio of the curing agent to the resin matrix in step 2a is 2-5:10 (can be any ratio of 1:5, 3:10, 2:5, 1:2, or a range corresponding to any two ratios);

[0013] D1: The stirring time during mixing in step 2a is 20-60 min (can be any value among 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min and 60 min, or a range corresponding to any two values);

[0014] E1: The molding process in step 2a is to add the mixed solution 2 into a closed mold with a thickness of 50-300 μm (any value among 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm and 300 μm or the range corresponding to any two values) for curing That is, a green body is obtained, wherein the curing time is 2-6 h (can be any value among 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h and 6 h, or a range corresponding to any two values), and the curing temperature is 100-200 ° C (can be any value among 100 ° C, 105 ° C, 110 ° C, 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195 ° C and 200 ° C or a range corresponding to any two values);

[0015] F1: In step 3a, the soaking time is 24-48h (can be any value among 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h and 48h, or a range between any two values), and the drying temperature is 30-80℃ (can be 30 ℃, 35℃, 40℃, 45℃, 55℃, 60℃, 65℃, 70℃, 75℃ and 80℃, or the range corresponding to any two values), and the drying time is 6-24h (it can be any value among 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h and 24h, or the range corresponding to any two values).

[0016] The resin matrix in the above technical solution is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, acrylic resin and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane;

[0017] The curing agent is an amine curing agent;

[0018] The pore-forming agent is at least one of polyethylene glycol, glucose, propylene carbonate, and N,N-dimethylformamide.

[0019] The bisphenol A epoxy resin described in the above technical solution is E51 type and / or E44 type bisphenol A epoxy resin;

[0020] The bisphenol F epoxy resin is Epikote 862 liquid bisphenol F epoxy resin;

[0021] The acrylic resin is JONCRYL 678 solid water-based acrylic resin;

[0022] The amine curing agent is at least one of D-400 curing agent, PACM curing agent, DDM curing agent and TETA curing agent.

[0023] The porous resin part described in the above technical solution is dried while being immersed in the Li ion solid electrolyte solution to accelerate volatilization, and the drying temperature is 40-70°C (it can be any value among 40°C, 45°C, 55°C, 60°C, 65°C and 70°C, or the corresponding range between any two values), and the drying time is more than 24h (the preferred drying time is 24-48h, which can be any value among 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h and 48h, or the corresponding range between any two values).

[0024] The preparation method of the Li ion solid electrolyte solution in the above technical solution comprises the following steps:

[0025] Step 1b: Activate oxalyl chloride by adding it to N,N-dimethylformamide containing dry acetonitrile;

[0026] Step 2b: adding the activated oxalyl chloride to 4-styrenesulfonic acid sodium salt to obtain 4-styrenesulfonyl chloride;

[0027] Step 3b: The obtained 4-styrenesulfonyl chloride is mixed with an equimolar amount of 4-(trifluoromethoxy)benzenesulfonamide to obtain a mixed solution III, which is concentrated to 1 / 10-1 / 5 of the original volume to obtain a brown substance, and the brown substance is dissolved in dichloromethane to obtain a mixed solution IV;

[0028] Step 4b: The mixed solution was washed with a NaHCO3 aqueous solution and a hydrochloric acid solution, and then evaporated to remove the solvent. The obtained concentrated solution was dried to obtain a dry solid, and the obtained substance was weighed;

[0029] Step 5b: dissolving the dry solid obtained above in a LiOH aqueous solution, stirring and reacting sufficiently to obtain 4-styrenesulfonyl (phenylsulfonyl) imide lithium salt;

[0030] Step 6b: adding 4-phenylsulfonyl (phenylsulfonyl) imide lithium salt to THF solution, centrifugally drying to obtain a solid Li salt electrolyte;

[0031] Step 7b: Dissolve the Li salt electrolyte in methyl sulfoxide and add PVDF-HFP to cross-link and blend to form a Li ion solid electrolyte solution.

[0032] The porous resin article described in the above technical solution must meet at least one of the following conditions during preparation:

[0033] A2: The molar ratio of oxalyl chloride to N,N-dimethylformamide in step 1b is 20-30:1;

[0034] B2: The molar ratio of oxalyl chloride to 4-styrenesulfonic acid sodium salt in step 2b is 0.5-0.5:1;

[0035] C2: The concentration of the NaHCO3 aqueous solution in step 4b is 3-5wt%, and its amount is 2-4 times the volume of the mixed solution;

[0036] D2: The concentration of the hydrochloric acid solution in step 4b is 0.8-1.2M, and the amount used is 3-5 times that of the mixed solution 4;

[0037] E2: Step 5b is dissolving the dried solid obtained above in a 0.9-1.3 times normal concentration of 0.4-0.6 M LiOH aqueous solution in a molar ratio;

[0038] F2: The mass ratio of Li salt electrolyte, methyl sulfoxide and PVDF-HFP in step 7b is 1:4-4.5:0.2-0.7.

[0039] A second object of the present invention is to provide an all-solid-state electrolyte having excellent performance and prepared by the above-mentioned preparation method.

[0040] A third object of the present invention is to provide an application of the all-solid-state electrolyte as described above as a separator in a button battery or a structural energy storage composite material.

[0041] Compared with the prior art, the beneficial effect of the present invention is that the all-solid-state electrolyte provided by the present invention can be used as a potential substitute for traditional liquid electrolytes, and its advantages are better safety, stability, a wider operating temperature range, higher energy density, better cycle performance and effective inhibition of lithium dendrite growth. This all-solid-state electrolyte can significantly improve the safety (because it does not contain solvent) and stability of the battery, and can be applied to the installation and application of solid-state electrolyte batteries. It has broad application prospects in many fields such as energy storage, sensor technology, micro-nanoelectronic devices, automobile manufacturing, and microelectronic products. The present invention introduces a Li ion solid electrolyte solution into the all-solid-state electrolyte pore structure (the Li ion solid electrolyte solution is immersed in the pores of the porous resin in the form of a solution, and then deposited and filled in the pores of the porous resin in the form of a volatilized solvent), and converts the porous resin into a solid structure of porous resin-all-solid-state electrolyte, which is beneficial to improving the overall mechanical properties of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the structure of the sheet sample in an embodiment of the present invention. DETAILED DESCRIPTION

[0043] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0044] Example 1

[0045] In the preparation of the porous resin in this embodiment, the mass ratio of the resin matrix to the pore-forming agent is 1:3, the mixing temperature of the resin matrix and the pore-forming agent is 25°C, and the stirring time is 0.2h; and the mass ratio of the curing agent to the resin matrix is 1:2, and the stirring time during mixing is 20min. The molding process is to add the mixed solution 2 into a closed mold for curing treatment to obtain a green body, wherein the curing time is 2h and the curing temperature is 180°C; the soaking time in step 3 is 24h, the drying temperature is 30°C, and the drying time is 24h, wherein the resin matrix is E44 bisphenol A epoxy resin, the curing agent is PACM curing agent, and the pore-forming agent is polyethylene glycol.

[0046] Example 2

[0047] The same as Example 1, except that, when prepared in the porous resin, the mass ratio of the resin matrix to the pore-forming agent is 1:2, the mixing temperature of the resin matrix and the pore-forming agent is 40°C, and the stirring time is 0.3h; the mass ratio of the curing agent to the resin matrix is 3:10, the stirring time during mixing is 30min, and the molding process is to add the mixed solution 2 into a closed mold for curing treatment to obtain a green body, wherein the curing time is 3h and the curing temperature is 150°C; the soaking time in step 3 is 30h, the drying temperature is 40°C, and the drying time is 10h, wherein the resin matrix is E51 bisphenol A epoxy resin, the curing agent is PACM curing agent, and the pore-forming agent is glucose.

[0048] Example 3

[0049] The same as Example 1, except that, when preparing in the porous resin, the mass ratio of the resin matrix to the pore-forming agent is 1:3, the mixing temperature of the resin matrix and the pore-forming agent is 50°C, and the stirring time is 0.4h; in step 2, the mass ratio of the curing agent to the resin matrix is 2:5, the stirring time during mixing is 40min, and the molding process is to add the mixed solution 2 into a closed mold for curing treatment to obtain a green body, wherein the curing time is 8h and the curing temperature is 100°C; in step 3, the soaking time is 35h, the drying temperature is 50°C, and the drying time is 15h, wherein the resin matrix is Epitome 862 liquid bisphenol F epoxy resin, the curing agent is DDM curing agent, and the pore-forming agent is propylene carbonate.

[0050] Example 4

[0051] The same as Example 1, except that, when preparing in the porous resin, the mass ratio of the resin matrix to the pore-forming agent is 1:4, the mixing temperature of the resin matrix and the pore-forming agent is 60°C, and the stirring time is 0.5h; in step 2, the mass ratio of the curing agent to the resin matrix is 1:2, the stirring time during mixing is 60min, and the molding process is to add the mixed solution 2 to a closed mold for curing treatment to obtain a green body, wherein the curing time is 6h and the curing temperature is 180°C; in step 3, the soaking time is 48h, the drying temperature is 80°C, and the drying time is 24h, wherein the resin matrix is JONCRYL 678 solid water-based acrylic resin, the curing agent is TETA curing agent, and the pore-forming agent is N,N-dimethylformamide.

[0052] Example 5

[0053] Preparation of Li-ion solid electrolyte solution

[0054] The preparation method of the Li ion solid electrolyte solution comprises the following steps:

[0055] Step 1: Activate by adding 25 mmol oxalyl chloride to 1 mmol N,N-dimethylformamide containing dry acetonitrile;

[0056] Step 2: Add the activated oxalyl chloride to 25 mmol 4-styrenesulfonic acid sodium salt to obtain 4-styrenesulfonyl chloride;

[0057] Step 3: The obtained 4-styrenesulfonyl chloride was mixed with an equal molar amount of 4-(trifluoromethoxy)benzenesulfonamide to obtain a mixed solution 3, and the mixture was evaporated and concentrated to 10 mL using a rotary evaporator at 45 degrees Celsius to obtain a brown substance, which was then dissolved in a dichloromethane solution to obtain a mixed solution 4;

[0058] Step 4: The mixture was washed with 4 wt% aqueous NaHCO3 solution (80 mL) and 1 M hydrochloric acid (40 mL), and the solvent was removed by rotary evaporation. The concentrated solution was placed in a vacuum oven at 60°C and dried for 24 h to obtain a dry solid, which was then weighed.

[0059] Step 5: The dried solid obtained above was reacted with an equivalent of 0.5 mL of iOH in water in a molar ratio and stirred for 24 hours to obtain 4-styrenesulfonyl (phenylsulfonyl) imide lithium salt;

[0060] Step 6: Add 4-phenylsulfonyl (phenylsulfonyl) imide lithium salt to THF solution and centrifuge to obtain a solid Li salt electrolyte;

[0061] Step 7: Dissolve the Li salt electrolyte in methyl sulfoxide and add PVDF-HFP cross-linking blend (mixed at a mass ratio of 1:4.26:0.5) to form a Li ion solid electrolyte solution.

[0062] Performance Test 1

[0063] Dumbbell-shaped films (narrow in the middle and wide at both ends) were prepared according to the preparation processes of Examples 1 to 4, and were designated as Film 1, Film 2, Film 3, and Film 4 for standby use.

[0064] Taking multiple sheets of film 1, film 2, film 3 and film 4, respectively, and immersing them in the Li ion solid electrolyte solution prepared in Example 5 to prepare an all-solid-state electrolyte, respectively obtaining an all-solid-state electrolyte 1, an all-solid-state electrolyte 2, an all-solid-state electrolyte 3 and an all-solid-state electrolyte 4 for standby use;

[0065] In accordance with the standard GB / T1040 for the determination of tensile properties of plastics, the LE5000 series electronic universal testing machine was used to test the above-mentioned film one, film two, film three, film four, all-solid electrolyte one, all-solid electrolyte two, all-solid electrolyte three and all-solid electrolyte four respectively. The specific test method is as follows: Place the sample in the fixture of the testing machine, ensure that the clamping area is completely fixed and the clamping position is centered. The central axis of the sample is aligned with the loading axis to avoid eccentric force, and the tensile rate is set according to the following: tensile rate: the chuck movement speed is 2mm / min; the test sample is a dumbbell-shaped sheet structure, and its shape is as follows: Figure 1 As shown, the thickness is 2mm, and the two ends are widened. The length of the widened part is b, the width is c, and the length of the middle effective section is a, where a is about 30mm, b is about 20mm, c is about 10mm, and the width of the middle effective section is 3-5mm (5mm is preferred).

[0066] At the same time, the electrical performance of samples of the prepared all-solid electrolyte 1, all-solid electrolyte 2, all-solid electrolyte 3, and all-solid electrolyte 4 was tested as the electrolyte portion of button cells. Using lithium iron phosphate as the positive electrode and graphite as the negative electrode, the charge and discharge capacity was primarily tested. The specific capacity (mAh / g) and the decay percentage after 100 cycles were calculated from the discharge capacity. The specific results are shown in Table 1:

[0067] Table 1 is a performance test table of the corresponding thin films and all-solid electrolytes of Examples 1 to 4

[0068] Mechanical properties MPa Specific capacity mAh / g 100 turns attenuation percentage Film 1 15.01 - - Film 2 18.50 - - Film three 16.69 - - Film 4 10.25 - - All-solid-state electrolyte 19.53 96.31 92.28％ All-solid-state electrolyte II 22.60 56.29 81.02％ All-solid-state electrolyte 3 20.18 97.36 92.59％ All-solid-state electrolyte 4 14.45 97.07 92.31％

[0069] As shown in the table above, the mechanical properties of Film 3 reached 16.69 MPa, while those of All-Solid Electrolyte 3 reached 20.18 MPa. The specific capacity reached 97.36 mAh / g, and the decay percentage after 100 cycles was 92.59%. This shows that Film 3 maintains relatively good mechanical properties while maintaining a high specific capacity, and the retention rate after 100 cycles is also good. Furthermore, the above series of tests show that the mechanical properties of the materials are significantly improved after the all-solid-state electrolyte is introduced into the porous resin.

[0070] Note: Films 1 to 4 are pure resins with no electrochemical properties, so their specific capacity and 100-cycle attenuation percentage were not tested.

[0071] Performance Test 2

[0072] According to the porous resin preparation process of Examples 1 to 4 and with reference to the preparation process of the structural energy storage composite material, porous resin blocks were prepared, each having a size of 250 mm in length, 15 mm in width, and 2 mm in thickness, and they were respectively prepared as block 1, block 2, block 3, and block 4 for standby use;

[0073] The general preparation process of structural energy storage composite materials is as follows:

[0074] The active material powders of positive electrode lithium iron phosphate and negative electrode graphite, a binder and a conductive agent are added in a N-methylpyrrolidone solvent in a mass ratio of 8:1:1 in sequence to obtain a slurry, wherein the weight ratio of the solvent to the material is 2.6:1; the stirred slurry is coated on the carbon fiber by a blade coating method at a thickness of 30-40 μm; dried at 90°C until the solvent is completely volatilized; finally, the slurry is cut to the required size and assembled into a laminated structure according to the form of the positive electrode, separator, and negative electrode; the epoxy resin, curing agent, and pore-forming agent prepared in the above embodiment are mixed by a drainage method. The liquid is introduced into the laminated structure (i.e., the porous resin is introduced in situ), and is cured by a corresponding curing process, the pore-forming agent is removed by foaming, and the structure is dried; the structural energy storage composite material is immersed in the solid electrolyte solution prepared in Example 5, and dried to obtain a structural energy storage composite material with an internal pore structure (the porous resin introduced in the structural energy storage composite material one corresponds to Example 1, the porous resin introduced in the structural energy storage composite material two corresponds to Example 2, the porous resin introduced in the structural energy storage composite material three corresponds to Example 3, and the porous resin introduced in the structural energy storage composite material four corresponds to Example 4).

[0075] According to the above process methods, specimens for electrical performance testing and mechanical performance testing are prepared respectively. The size of the structural energy storage composite material sample used for the electrical performance test is a 4×4 cm cube structure; the blocks containing porous resin but not filled with solid electrolyte and the structural energy storage composite material with porous resin filled with solid electrolyte used for the mechanical performance test are prepared in accordance with the composite material-tensile test method standard ASTMD3039. Tensile test specimens are prepared and tested using an LE5000 series electronic universal testing machine. The specific test methods can be carried out according to the standard.

[0076] Similarly, the mechanical properties of block 1, block 2, block 3, block 4, structural energy storage composite material 1, structural energy storage composite material 2, structural energy storage composite material 3 and structural energy storage composite material 4 were tested. The specific results are shown in Table 2:

[0077] Table 2 is the performance test table of the corresponding block and structure energy storage composite materials of Examples 1 to 4

[0078] Mechanical properties MPa Block 1 185.30 Block 2 211.25 Block Three 191.09 Block Four 130.57 Structural energy storage composite materials 216.30 Structural Energy Storage Composite Materials II 254.38 Structural Energy Storage Composite Materials III 217.26 Structural Energy Storage Composite Materials IV 150.69

[0079] The electrochemical performance of each structure energy storage composite material was tested and characterized using a blue electric system; the specific results are shown in Table 3:

[0080] Table 3 is the performance test table of the energy storage composite materials corresponding to Examples 1 to 4

[0081] Specific capacity mAh / g 100 turns attenuation percentage Structural energy storage composite materials 98.64 76.07％ Structural Energy Storage Composite Materials II 67.78 47.80％ Structural Energy Storage Composite Materials III 104.11 77.24％ Structural Energy Storage Composite Materials IV 103.08 77.09％

[0082] As shown in the table above, the mechanical properties of Block 3 reached 191.09 MPa, and those of Structural Energy Storage Composite Material 1 reached 254.38 MPa. Furthermore, the electrical test sample prepared using this method achieved a specific capacity of 104.11 mAh / g, with a decay percentage of 77.24% after 100 cycles. This indicates that Structural Energy Storage Composite Material 3 maintains excellent mechanical properties while maintaining excellent electrical performance. Furthermore, these tests demonstrate that the mechanical properties of the porous resin-structural energy storage composite material are significantly improved by introducing an all-solid-state electrolyte into the material.

[0083] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing an all-solid-state electrolyte, characterized in that: The porous resin part is immersed in a Li-ion solid electrolyte solution, and a fully solid electrolyte is obtained after the solvent evaporates.

2. The method for preparing an all-solid-state electrolyte according to claim 1, wherein: The method for preparing the porous resin component comprises the following steps: Step 1a: mixing the resin matrix and the pore-forming agent to form a uniform mixed solution; Step 2a: adding a curing agent to the mixed solution 1, mixing to obtain a mixed solution 2, and molding the mixed solution 2 to obtain a green body; Step 3a: Soak the green body in deionized water, then take it out and dry it to obtain a porous resin part.

3. The method for preparing the all-solid-state electrolyte according to claim 2, wherein: The porous resin component must meet at least one of the following conditions during preparation: A1: The mass ratio of the resin matrix to the pore-forming agent in step 1a is 1:1-4; B1: In step 1a, the temperature of mixing the resin matrix and the pore-forming agent is 25-60°C, and the stirring time is 0.2-0.5h; C1: The mass ratio of curing agent to resin matrix in step 2a is 2-5:10; D1: The stirring time during mixing in step 2a is 20-60 minutes; E1: The molding process in step 2a is to add the mixed solution 2 into a closed mold for curing to obtain a green body, wherein the curing time is 2-6 hours and the curing temperature is 100-180°C; F1: In step 3a, the soaking time is 24-48 hours, the drying temperature is 30-80°C, and the drying time is 6-24 hours.

4. The method for preparing an all-solid-state electrolyte according to claim 2, wherein: The resin matrix is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, acrylic resin and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane; The curing agent is an amine curing agent; The pore-forming agent is at least one of polyethylene glycol, glucose, propylene carbonate, and N,N-dimethylformamide.

5. The method for preparing the all-solid-state electrolyte according to claim 4, wherein: The bisphenol A epoxy resin is E51 type and / or E44 type bisphenol A epoxy resin; The bisphenol F epoxy resin is Epikote 862 liquid bisphenol F epoxy resin; The acrylic resin is JONCRYL 678 solid water-based acrylic resin; The amine curing agent is at least one of D-400 curing agent, PACM curing agent, DDM curing agent and TETA curing agent.

6. The method for preparing an all-solid-state electrolyte according to claim 1, wherein: The porous resin component is dried while being immersed in the Li ion solid electrolyte solution to accelerate volatilization. The drying temperature is 40-70° C. and the drying time is more than 24 hours.

7. The method for preparing an all-solid-state electrolyte according to claim 1, wherein: The preparation method of the Li ion solid electrolyte solution comprises the following steps: Step 1b: Activate oxalyl chloride by adding it to N,N-dimethylformamide containing dry acetonitrile; Step 2b: adding the activated oxalyl chloride to 4-styrenesulfonic acid sodium salt to obtain 4-styrenesulfonyl chloride; Step 3b: The obtained 4-styrenesulfonyl chloride is mixed with an equimolar amount of 4-(trifluoromethoxy)benzenesulfonamide to obtain a mixed solution III, which is concentrated to 1 / 10-1 / 5 of the original volume to obtain a brown substance, and the brown substance is dissolved in dichloromethane to obtain a mixed solution IV; Step 4b: The mixed solution was washed with a NaHCO3 aqueous solution and a hydrochloric acid solution, and then evaporated to remove the solvent. The obtained concentrated solution was dried to obtain a dry solid, and the obtained substance was weighed; Step 5b: dissolving the dry solid obtained above in a LiOH aqueous solution, stirring and reacting sufficiently to obtain 4-styrenesulfonyl (phenylsulfonyl) imide lithium salt; Step 6b: adding 4-phenylsulfonyl (phenylsulfonyl) imide lithium salt to THF solution, centrifugally drying to obtain a solid Li salt electrolyte; Step 7b: Dissolve the Li salt electrolyte in methyl sulfoxide and add PVDF-HFP to cross-link and blend to form a Li ion solid electrolyte solution.

8. The method for preparing the all-solid-state electrolyte according to claim 7, characterized in that: The porous resin component must meet at least one of the following conditions during preparation: A2: The molar ratio of oxalyl chloride to N,N-dimethylformamide in step 1b is 20-30:1; B2: The molar ratio of oxalyl chloride to 4-styrenesulfonic acid sodium salt in step 2b is 0.5-0.5:1; C2: The concentration of the NaHCO3 aqueous solution in step 4b is 3-5wt%, and its amount is 2-4 times the volume of the mixed solution; D2: The concentration of the hydrochloric acid solution in step 4b is 0.8-1.2M, and the amount used is 3-5 times that of the mixed solution 4; E2: Step 5b is dissolving the dried solid obtained above in a 0.9-1.3 times normal concentration of 0.4-0.6 M LiOH aqueous solution in a molar ratio; F2: The mass ratio of Li salt electrolyte, methyl sulfoxide and PVDF-HFP in step 7b is 1:4-4.5:0.2-0.

7.

9. An all-solid-state electrolyte, characterized in that The method is as described in any one of claims 1 to 8.

10. A use of the all-solid electrolyte according to claim 9, characterized in that: The all-solid-state electrolyte is used as a separator in a button battery or as a structural energy storage composite material.

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