Solid-state energy storage battery based on high-performance solid-state electrolyte and preparation method and application thereof

Abstract

This invention relates to the field of solid-state battery technology, specifically to a solid-state energy storage battery based on a high-performance solid-state electrolyte, its preparation method, and its application. It addresses the problems of low conductivity and short cycle life inherent in existing solid-state electrolyte materials. The battery employs an all-solid-state structure, eliminating the flammable and leak-prone liquid organic electrolyte found in traditional batteries, thus preventing thermal runaway, fire, and explosion. The solid-state electrolyte possesses higher mechanical strength, physically blocking and effectively inhibiting the piercing growth of sodium dendrites, avoiding internal short circuits caused by this. The cathode material used exhibits minimal volume change and high structural stability during charging and discharging. The interface formed between the solid-state electrolyte and the electrode avoids the persistent side reactions present in the liquid system, resulting in excellent cycle life under high-frequency cycling conditions such as start-stop.

Description

Technical Field

[0001] This invention relates to the field of solid-state battery technology, specifically to solid-state energy storage batteries based on high-performance solid-state electrolytes, their preparation methods, and applications. Background Technology

[0002] Solid-state batteries, as a novel energy storage technology, have received widespread attention in recent years. Compared with traditional liquid batteries, solid-state batteries use solid electrolytes instead of flammable liquid electrolytes, significantly improving battery safety and energy density. Solid electrolytes are one of the core components of solid-state batteries, and their performance directly affects the battery's efficiency and lifespan. Commonly used solid electrolyte materials include oxides, sulfides, and polymers, which can provide better ionic conductivity and thermal stability. Solid electrolytes in solid-state batteries can effectively prevent leakage and thermal runaway problems, thus having broad application prospects in electric vehicles, drones, and portable electronic devices.

[0003] High-performance solid electrolytes are key to solid-state battery technology. Existing solid electrolyte materials suffer from low ionic conductivity, which greatly limits the charge-discharge efficiency and energy density of batteries. At the same time, the interfacial stability between the electrolyte and the battery electrodes is difficult to improve, resulting in shortened battery cycle life and performance degradation. The manufacturing cost and large-scale production process of high-performance solid electrolytes are also not mature enough, which limits their widespread application in practical applications. Therefore, the mechanical strength and thermal stability of solid electrolytes have become the focus of research.

[0004] Therefore, the development of solid-state energy storage batteries based on high-performance solid-state electrolytes, their preparation methods, and applications are of great significance in the field of solid-state battery technology. Summary of the Invention

[0005] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide a solid-state energy storage battery based on a high-performance solid-state electrolyte, its preparation method and application: it solves the problems that existing solid-state electrolyte materials have low ionic conductivity, which limits the charge and discharge efficiency and energy density of the battery, and poor interface stability between the electrolyte and the battery electrode, which leads to a short battery cycle life.

[0006] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a solid-state energy storage battery based on a high-performance solid-state electrolyte, comprising the following components in parts by weight: 70-80 parts of positive electrode material, 8-15 parts of conductive carbon black, 5-10 parts of polyvinylidene fluoride, 5-10 parts of positive electrode current collector, 150-200 parts of solid electrolyte membrane, 130-150 parts of negative electrode material, and 30-50 parts of negative electrode current collector. The conductive carbon black is of type ENSACO 250G; the polyvinylidene fluoride is of type HSV900; the positive electrode current collector is copper foil; the negative electrode material is sodium sheet; and the negative electrode current collector is aluminum foil.

[0007] In a preferred embodiment of the present invention, the positive electrode material is prepared by the following steps: Step a1: Add triethylene glycol monomethyl ether and Raney nickel to a reaction vessel, purge the air in the vessel with nitrogen, purge with ammonia until saturated, purge with hydrogen at 1-3 MPa, heat to 205°C, mix and stir for 25-35 h, cool naturally to 25°C, adjust the pH to 2-3 with hydrochloric acid solution, distill under reduced pressure, add sodium hydroxide solution, mix and stir for 30 min, extract with dichloromethane 2-3 times, combine the organic phases, add anhydrous magnesium sulfate and dry for 10-15 min, filter, concentrate by rotary evaporation for 15-30 min, fractionate under vacuum, collect the distillate, and obtain triethylene glycol monomethyl ether amine;

[0008] Step a2: Triethylene glycol monomethyl etheramine, tris(dibenzylacetone)dipalladium, sodium tert-butoxide, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and toluene were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was subjected to a "freezing-vacuuming-thawing" cycle three times. 4-bromo-2-fluoro-1-iodobenzene was added at 25°C under nitrogen protection. The mixture was stirred at 50°C and 300 rpm for 20-24 hours. After cooling to 25°C, the mixture was poured into a beaker containing ammonium chloride solution for quenching. The mixture was separated using a separatory funnel. The aqueous phase was extracted 2-3 times with ethyl acetate. The organic phases were combined and dried with anhydrous magnesium sulfate for 10-15 minutes. The mixture was then concentrated in a rotary evaporator at 30-35°C for 15-30 minutes. Eluent was added, and the mixture was purified by alumina column chromatography to obtain the aniline derivative.

[0009] Step a3: Under 0℃ ice bath and nitrogen protection, ethyl magnesium bromide, aniline derivatives and tetrahydrofuran are added to a three-necked flask equipped with a stirrer and thermometer. The mixture is stirred for 10-15 min, heated to 25-35℃ and vacuum rotary evaporated for 1-2 h. Ferrous chloride, 1,2-dibromoethane and toluene are added. The mixture is stirred at 400-500 r / min for 12 h under nitrogen protection and 100℃. After the reaction is completed, the mixture is naturally cooled to 25℃, quenched with deionized water, extracted with dichloromethane 2-3 times, and the organic phase is washed 1-2 times with sodium chloride solution. Anhydrous magnesium sulfate is added and dried for 10-15 min. The mixture is then evaporated and concentrated at 20-25℃ for 5-15 min to obtain the intermediate.

[0010] Step a4: Add 5,10-dihydrophenazine, the intermediate, sodium tert-butoxide, and the first portion of xylene to a three-necked flask equipped with a stirrer and thermometer, and sonicate to degas for 5-10 minutes to obtain the first solution; mix palladium acetate, 2-bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl, and the second portion of xylene at 25°C and stir for 5-10 minutes to obtain the second solution; under nitrogen protection, add the second solution to the first solution and perform "freezing- The reaction was carried out in a vacuum-thawing cycle three times. The mixture was stirred at 600 r / min at 120℃ for 24 h, and then stirred at 140℃ for 12 h. The temperature was lowered to 120℃, bromobenzene was added, and the mixture was stirred for another 5-6 h. The mixture was then allowed to cool naturally to 25℃, a mixed solvent was added, and the mixture was stirred for 30 min. The mixture was filtered, and the filter cake was washed 2-3 times with o-xylene, tetrahydrofuran, and acetonitrile in sequence. The cake was then transferred to a vacuum drying oven at 60℃ and dried for 24 h to obtain the cathode material.

[0011]

[0012] In a preferred embodiment of the present invention, the ratio of triethylene glycol monomethyl ether, Raney nickel, sodium hydroxide solution and anhydrous magnesium sulfate in step a1 is 40-50 mL: 4-5 g: 80-100 mL: 10-15 g; the concentration of the hydrochloric acid solution is 2 mol / L; and the mass fraction of the sodium hydroxide solution is 50%.

[0013] In a preferred embodiment of the present invention, the ratio of triethylene glycol monomethyl etheramine, tris(dibenzylacetone)dipalladium, sodium tert-butoxide, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, toluene, 4-bromo-2-fluoro-1-iodobenzene, ammonium chloride solution, anhydrous magnesium sulfate, and eluent in step a2 is 3-4 mL : 0.5-0.6 g : 3.5-4 g : 0.4-0.6 g : 80-100 mL : 5-7 g : 100 mL : 5-10 g : 500-1000 mL; the mass fraction of the ammonium chloride solution is 26%; and the eluent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 5-10:1.

[0014] In a preferred embodiment of the present invention, the ratio of the amounts of ethyl magnesium bromide, aniline derivative, tetrahydrofuran, ferrous chloride, 1,2-dibromoethane, toluene, deionized water, dichloromethane, and anhydrous magnesium sulfate in step a3 is 10-15 mL: 3-5 g: 15-20 mL: 5-15 mg: 1-3 mL: 30 mL: 50 mL: 90 mL: 5-10 g; and the mass fraction of the sodium chloride solution is 26%.

[0015] In a preferred embodiment of the present invention, the ratio of the amounts of 5,10-dihydrophenazine, intermediate, sodium tert-butoxide, total xylene, palladium acetate, 2-dicyclohexylphosphine-2,4',6'-triisopropylbiphenyl, bromobenzene, and mixed solvent in step a4 is 0.1-0.2g:0.4-0.5g:0.2-0.3g:40mL:10-15mg:40-50mg:0.5-1mL:200mL; the first part of xylene accounts for 5 / 8 of the total amount of xylene; the second part of xylene accounts for 3 / 8 of the total amount of xylene; the mixed solvent is prepared by mixing methanol and acetone in a volume ratio of 1:1.

[0016] In a preferred embodiment of the present invention, the solid electrolyte membrane is prepared by the following steps: Step b1: Add zirconium nitrate pentahydrate, tetraethyl silicate, ammonium dihydrogen phosphate, sodium nitrate, and ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Add a complexing agent and magnetically stir at 300 r / min for 6-8 h. Place in an 80°C water bath and continue stirring at 200 r / min for 3-4 h. Transfer to a 120°C forced-air drying oven and dry for 10-12 h. Place in a muffle furnace and sinter at 350°C for 4 h in an air atmosphere at a rate of 2-3°C / min. Grind in a mortar and continue heating at 900°C for 12 h at a rate of 5°C / min. Allow to cool naturally to 25°C. Add to a planetary ball mill with a ball-to-material ratio of 10:1. Add anhydrous ethanol and ball mill at 350 r / min for 5-8 h. Dry at 80°C for 5-6 h. After grinding, sieve through a 400-mesh sieve to obtain crystalline powder. Step b2: Add the crystalline powder and ethanol solution to a three-necked flask equipped with a stirrer and thermometer, sonicate for 30 min, place in an oil bath at 75°C, stir at 400 r / min for 30 min, adjust the pH to 11 with ammonia, continue stirring and activating for 1 h to obtain a suspension; add methoxy polyethylene glycol silane and anhydrous ethanol to a beaker and mix and stir for 30 min, add the above suspension, stir and react at 75°C and 400 r / min for 6-8 h, transfer to a dialysis bag with a molecular weight cutoff of 8000-14000 and dialyze for 72 h, freeze-dry at -50°C for 24-48 h to obtain the functional filler; Step b3: Add the first part of polyvinylidene fluoride-hexafluoropropylene copolymer, sodium perchlorate, and N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Stir magnetically at 500 r / min for 6-8 h at 50 °C, let stand for 30 min to degas, cast into a film using a casting machine, and transfer to a 60 °C forced-air drying oven to dry for 6 h to obtain a support membrane. Mix and ultrasonically disperse the functional filler and acetonitrile for 1 h, add sodium bis(trifluoromethanesulfonyl)imide, stir magnetically at 400 r / min for 2-3 h, add polyethylene oxide and the second part of polyvinylidene fluoride-hexafluoropropylene copolymer, stir at 300-600 r / min for 48-72 h, let stand for 30 min to degas, cast into a film on the surface of the support membrane, let stand at 25 °C for 12 h, and transfer to a 50-60 °C vacuum drying oven to dry for 24-48 h to obtain a solid electrolyte membrane.

[0017] In a preferred embodiment of the present invention, the ratio of zirconium nitrate pentahydrate, tetraethyl silicate, ammonium dihydrogen phosphate, sodium nitrate, ethanol solution, complexing agent, and anhydrous ethanol in step b1 is 10-13g: 5-10mL: 3-4g: 4-5g: 125mL: 15-17g: 80-100mL; the mass fraction of the ethanol solution is 75%; and the complexing agent is citric acid.

[0018] In a preferred embodiment of the present invention, the ratio of the crystalline powder, ethanol solution, methoxy polyethylene glycol silane, and anhydrous ethanol in step b2 is 5-6g:100mL:5-6mL:10mL; the mass fraction of the ethanol solution is 90%; and the methoxy polyethylene glycol silane is of type P001012 with a molecular weight of 2K.

[0019] In a preferred embodiment of the present invention, the ratio of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer, sodium perchlorate, N,N-dimethylformamide, functional filler, acetonitrile, sodium bis(trifluoromethanesulfonyl)imide, and polyethylene oxide in step b3 is 1.2-2.4g: 0.4-0.8g: 20mL: 0.15-0.3g: 10mL: 0.4-0.6g: 0.4-0.6g; the polyvinylidene fluoride-hexafluoropropylene copolymer is produced by Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., with product number lnb-1003; the polyethylene oxide is produced by Aladdin brand, with product number P432437; the first part of polyvinylidene fluoride-hexafluoropropylene copolymer accounts for 2 / 3 of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer; the second part of polyvinylidene fluoride-hexafluoropropylene copolymer accounts for 1 / 3 of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer.

[0020] Secondly, this application provides a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, including the following steps: Step 1: Weigh out the following components by weight: 70-80 parts of positive electrode material, 8-15 parts of conductive carbon black, 5-10 parts of polyvinylidene fluoride, 80-100 parts of N-methyl-2-pyrrolidone, 5-10 parts of positive electrode current collector, 150-200 parts of solid electrolyte membrane, 130-150 parts of negative electrode material, and 30-50 parts of negative electrode current collector. Step 2: Add the positive electrode material, conductive carbon black, polyvinylidene fluoride, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 minutes to obtain a positive electrode slurry. Coat the positive electrode slurry onto the positive electrode current collector and dry it in a vacuum at 60°C for 12 hours. Then cut it into discs as positive electrode sheets. Punch the solid electrolyte membrane into discs and place them on a hot press. Press them at 60°C and 5MPa for 2-3 minutes. Place the negative electrode material on the negative electrode current collector and roll it with a roller press. Punch it into discs to obtain a negative electrode sheet. Stack the positive electrode sheet, solid electrolyte membrane, and negative electrode sheet from bottom to top. Press and seal them with a constant pressure of 500-750MPa. Let them stand at 25°C for 24 hours to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0021] Thirdly, this application provides the application of solid-state energy storage batteries based on high-performance solid-state electrolytes in electric vehicles, drones, and portable electronic devices, as described in the first aspect.

[0022] The beneficial effects of this invention are: This invention relates to a solid-state energy storage battery based on a high-performance solid-state electrolyte, its preparation method, and its application. The method involves adding positive electrode material, conductive carbon black, polyvinylidene fluoride, and N-methyl-2-pyrrolidone to a centrifugal mixer and stirring to obtain a positive electrode slurry. The positive electrode slurry is then coated onto a positive electrode current collector, vacuum dried, and cut into discs to serve as positive electrode sheets. A solid electrolyte membrane is punched into discs and hot-pressed on a hot press. A negative electrode sheet is placed on a negative electrode current collector, rolled and punched into discs to obtain a negative electrode sheet. These discs are then stacked from bottom to top in the order of positive electrode sheet-solid electrolyte membrane-negative electrode sheet, pressed tightly and sealed, and left to stand to obtain a solid-state energy storage battery based on a high-performance solid-state electrolyte. This battery employs an all-solid-state structure. This design eliminates the flammable and leak-prone liquid organic electrolyte found in traditional batteries, preventing the possibility of thermal runaway, fire, and explosion. The solid-state electrolyte has higher mechanical strength, physically blocking and effectively inhibiting the piercing growth of sodium dendrites, thus avoiding internal short circuits. The positive electrode material exhibits small volume changes and high structural stability during charging and discharging. The interface formed between the solid-state electrolyte and the electrode avoids the side reactions that persist in the liquid system, resulting in excellent cycle life under high-frequency cycling conditions such as start-stop. The ether-oxygen side chains of the positive electrode enhance low-temperature interface compatibility, enabling the battery to maintain high proportional capacity and discharge capability at low temperatures. The all-solid-state design directly uses metallic sodium as the negative electrode, resulting in a capacity higher than that of traditional negative electrode materials.

[0023] In the preparation of a solid-state energy storage battery based on a high-performance solid-state electrolyte, a positive electrode material was first prepared. Using triethylene glycol monomethyl ether as a raw material, ammonia gas was introduced, and a catalytic amination reaction occurred under Raney nickel catalysis, converting the hydroxyl group of the alcohol to an amino group, yielding triethylene glycol monomethyl ether amine. Under the action of the catalyst tris(dibenzylacetone)dipalladium and the ligand 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, the amino-containing triethylene glycol monomethyl ether amine reacts with the iodine in 4-bromo-2-fluoro-1-iodobenzene to form a CN bond. Aniline derivatives were generated; a flexible triethylene glycol monomethyl ether side chain was introduced. This chain segment is rich in ether oxygen atoms, which have a strong coordination ability with sodium ions. In solid-state batteries, these side chains can serve as pathways for sodium ion transport within the cathode material, increasing the diffusion rate of ions within the active material and improving the rate performance of the battery. The chemical environment of this chain segment is similar to that of the solid electrolyte, which can reduce the interfacial resistance between the cathode particles and the solid electrolyte, ensuring efficient ion flow through the interface; the aniline derivative and ethyl... Magnesium bromide reacts to form a highly active magnesium amide salt. Under the catalysis of ferrous chloride, this amide salt reacts with 1,2-dibromoethane, undergoing intramolecular ring closure and bromination to yield an intermediate with a phenazine structure. The phenazine structure is a highly conjugated planar aromatic system, and its nitrogen atoms can undergo reversible redox reactions, serving as active sites for storing / releasing sodium ions, resulting in high theoretical capacity. In a palladium catalyst system (palladium acetate / 2-dicyclohexylphosphine-2,4',6'-triisopropylbiphenyl), the 5,10-dihydrophenazine monomer and the intermediate undergo alternating copolymerization, linked by CN bonds to form a polymer backbone. High-temperature reaction promotes intermolecular crosslinking, and bromobenzene capping yields the cathode material. This cathode material possesses a highly stable insoluble polymer network, avoiding the dissolution and loss of small-molecule organic electrode materials in the electrolyte, and exhibits a high cycle life. The polymer backbone is a continuous π-π conjugated system, providing channels for rapid electron delocalization and transport, significantly improving the intrinsic electronic conductivity of the material and reducing the battery's internal resistance.

[0024] In the preparation of a solid-state energy storage battery based on a high-performance solid-state electrolyte, a solid electrolyte membrane was first prepared. Zirconium nitrate pentahydrate, tetraethyl silicate, and ammonium dihydrogen phosphate underwent a hydrolysis-condensation reaction in solution to form a gel. After drying and sintering to remove organic matter and ammonium salts, the gel was then sintered at high temperature, resulting in a solid-phase reaction. Ball milling then broke the gel into powder, yielding crystalline powder. This crystalline powder exhibits high room-temperature ionic conductivity. Under alkaline conditions, the methoxy group in methoxy polyethylene glycol silane hydrolyzes to generate silanol groups. These silanol groups undergo dehydration condensation with the hydroxyl groups on the surface of the crystalline powder, forming stable Si-O-Si covalent bonds. Flexible polyethylene glycol long chains are then grafted onto the surface of the crystalline powder, yielding a functional filler. The polyethylene glycol long chains act as "molecular bridges," altering the surface properties of the crystalline powder, preventing agglomeration, and ensuring uniform dispersion. The polyethylene glycol chains have a similar chemical structure to polyoxyethylene esters, enabling… The filler and matrix are fused at the molecular level, eliminating inactive interfaces. Polyvinylidene fluoride-hexafluoropropylene copolymer and sodium perchlorate are dissolved in N,N-dimethylformamide and cast to form a support membrane. Functional fillers, sodium bis(trifluoromethanesulfonyl)imide, polyethylene oxide, and polyvinylidene fluoride-hexafluoropropylene copolymer are dissolved / dispersed in acetonitrile to obtain a functional layer slurry, which is cast onto the support membrane and dried. The two layers are bonded through the entanglement and penetration of polymer chains, resulting in a bilayer composite solid electrolyte membrane. The dense lower support membrane provides mechanical strength and inhibits sodium dendrite penetration, while the enriched upper membrane is responsible for efficient ion transport. The dispersed functional filler and polyethylene oxide slurry form a penetrating "filler-matrix" interpenetrating ion conduction network with high conductivity. The soft upper polyethylene oxide surface can form close contact with the positive and negative electrodes, reducing interfacial impedance and exhibiting high interfacial stability. Attached Figure Description

[0025] The invention will now be further described with reference to the accompanying drawings.

[0026] Figure 1 This is a schematic diagram of the cycle stability (1C rate, capacity retention after 1000 cycles) test results of the solid-state energy storage batteries of Examples 1-3 and Comparative Examples 1-3 in this invention.

[0027] Figure 2 This is a schematic diagram showing the conductivity test results of the solid-state energy storage batteries in Examples 1-3 and Comparative Examples 1-3 of this invention. Detailed Implementation

[0028] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1:

[0030] This embodiment describes a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, including the following steps: Step S1: Add 40 mL of triethylene glycol monomethyl ether and 4 g of Raney nickel to the reaction vessel, purge the air in the vessel with nitrogen, purge with ammonia until saturated, purge with 1 MPa of hydrogen, heat to 205 °C, mix and stir for 25 h, cool naturally to 25 °C, adjust the pH to 2 with 2 mol / L hydrochloric acid solution, distill under reduced pressure, add 80 mL of 50% sodium hydroxide solution, mix and stir for 30 min, extract twice with dichloromethane, combine the organic phases, add 10 g of anhydrous magnesium sulfate and dry for 10 min, filter, concentrate by rotary evaporation for 15 min, vacuum fractionate, collect the distillate, and obtain triethylene glycol monomethyl ether amine; Step S2: Add 3 mL of triethylene glycol monomethyl etheramine, 0.5 g of tris(dibenzylacetone)dipalladium, 3.5 g of sodium tert-butoxide, 0.4 g of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 80 mL of toluene to a three-necked flask equipped with a stirrer and thermometer. Perform a "freezing-vacuuming-thawing" cycle three times. Add 5 g of [unspecified substance] under nitrogen protection at 25°C. 4-Bromo-2-fluoro-1-iodobenzene was stirred at 50℃ and 300 r / min for 20 h, cooled to 25℃, and quenched in a beaker containing 100 mL of 26% ammonium chloride solution. The mixture was separated using a separatory funnel, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, dried for 10 min with 5 g of anhydrous magnesium sulfate, and concentrated by evaporation at 30℃ for 15 min in a rotary evaporator. 500 mL of an eluent consisting of a 5:1 volume ratio of petroleum ether and ethyl acetate was added, and the mixture was purified by alumina column chromatography to obtain the aniline derivative. Step S3: Under 0℃ ice bath and nitrogen protection, 10 mL of ethyl magnesium bromide, 3 g of aniline derivative and 15 mL of tetrahydrofuran were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred for 10 min, heated to 25℃ and vacuum rotary evaporated for 1 h. 5 mg of ferrous chloride, 1 mL of 1,2-dibromoethane and 30 mL of toluene were added. The mixture was stirred at 400 r / min for 12 h under nitrogen protection and 100℃. After the reaction was completed, the mixture was naturally cooled to 25℃, quenched with 50 mL of deionized water, extracted twice with 90 mL of dichloromethane, and washed once with 26% sodium chloride solution. 5 g of anhydrous magnesium sulfate was added and dried for 10 min. The mixture was then evaporated and concentrated at 20℃ for 5 min to obtain the intermediate. Step S4: Add 0.1g of 5,10-dihydrophenazine, 0.4g of the intermediate, 0.2g of sodium tert-butoxide, and 25mL of xylene to a three-necked flask equipped with a stirrer and thermometer, and sonicate for 5 minutes to obtain the first solution; mix and stir 10mg of palladium acetate, 40mg of 2-bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl, and 15mL of xylene at 25°C for 5 minutes to obtain the second solution; under nitrogen protection, add the second solution to the first solution and perform a three-cycle "freezing-vacuuming-thawing". The reaction was carried out at 120℃ with stirring at 600 r / min for 24 h, and then at 140℃ with stirring for 12 h. The temperature was lowered to 120℃, 0.5 mL of bromobenzene was added, and the reaction was stirred for another 5 h. The mixture was then allowed to cool naturally to 25℃, and 200 mL of a mixed solvent consisting of methanol and acetone in a 1:1 volume ratio was added. The mixture was stirred for 30 min, filtered, and the filter cake was washed twice with o-xylene, tetrahydrofuran, and acetonitrile in sequence. The cake was then transferred to a vacuum drying oven at 60℃ and dried for 24 h to obtain the cathode material. Step S5: Add 10g zirconium nitrate pentahydrate, 5mL tetraethyl silicate, 3g ammonium dihydrogen phosphate, 4g sodium nitrate, and 125mL of 75% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Add 15g citric acid and stir magnetically at 300r / min for 6 hours. Place the flask in an 80℃ water bath and continue stirring at 200r / min for 3 hours. Transfer the flask to a 120℃ drying oven and dry for 10 hours. Placed in a muffle furnace, sintered at 350℃ for 4 hours at a rate of 2℃ / min under air atmosphere. Then, it was ground in a mortar and sintered at 900℃ for 12 hours at a rate of 5℃ / min. After natural cooling to 25℃, it was placed in a planetary ball mill with a ball-to-material ratio of 10:1. 80 mL of anhydrous ethanol was added, and the mixture was ball-milled at 350 r / min for 5 hours. After drying at 80℃ for 5 hours, the powder was sieved through a 400-mesh sieve to obtain crystalline powder. Step S6: Add 5g of crystalline powder and 100mL of 90% ethanol solution to a three-necked flask equipped with a stirrer and thermometer, sonicate for 30min, place in an oil bath at 75℃, stir at 400r / min for 30min, adjust the pH to 11 with ammonia, continue stirring and activating for 1h to obtain a suspension; add 5mL of methoxy polyethylene glycol silane P001012-2K and 10mL of anhydrous ethanol to a beaker and mix and stir for 30min, add the above suspension, stir and react at 75℃ and 400r / min for 6h, transfer to a dialysis bag with a molecular weight cutoff of 8000 and dialyze for 72h, freeze-dry at -50℃ for 24h to obtain the functional filler; Step S7: Add 0.8g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, 0.4g of sodium perchlorate, and 20mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Stir magnetically at 500r / min for 6 hours at 50℃, allow to stand for 30 minutes to degas, and then cast into a film using a casting machine. Transfer the film to a 60℃ forced-air drying oven and dry for 6 hours to obtain a supported film. Mix 0.15g of functional filler and 10mL of acetonitrile and ultrasonically disperse. 1 h, add 0.4 g of sodium bis(trifluoromethanesulfonyl)imide, stir magnetically at 400 r / min for 2 h, add 0.4 g of polyethylene oxide P432437 and 0.4 g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, stir at 300 r / min for 48 h, let stand to degas for 30 min, cast on the surface of the support membrane to form a film, let stand at 25 ℃ for 12 h, transfer to a vacuum drying oven at 50 ℃ and dry for 24 h to obtain a solid electrolyte membrane; Step S8: Weigh out 70 parts of positive electrode material, 8 parts of conductive carbon black ENSACO 250G, 5 parts of polyvinylidene fluoride HSV900, 80 parts of N-methyl-2-pyrrolidone, 5 parts of copper foil, 150 parts of solid electrolyte membrane, 130 parts of sodium sheet and 30 parts of aluminum foil according to the following weight. Step S9: Add the positive electrode material, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto a copper foil, dry it in a vacuum at 60°C for 12 h, and then cut it into discs as positive electrode sheets; punch the solid electrolyte membrane into discs, place them on a hot press, and hot press them at 60°C and 5 MPa for 2 min; place the sodium sheet on an aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it with a constant pressure of 500 MPa, and let it stand at 25°C for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0031] Example 2:

[0032] This embodiment describes a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, including the following steps: Step S1: Add 45 mL of triethylene glycol monomethyl ether and 4.5 g of Raney nickel to the reaction vessel, purge the air in the vessel with nitrogen, purge with ammonia until saturated, purge with 2 MPa of hydrogen, heat to 205 °C, mix and stir for 30 h, cool naturally to 25 °C, adjust the pH to 3 with 2 mol / L hydrochloric acid solution, distill under reduced pressure, add 90 mL of 50% sodium hydroxide solution, mix and stir for 30 min, extract three times with dichloromethane, combine the organic phases, add 13 g of anhydrous magnesium sulfate and dry for 13 min, filter, concentrate by rotary evaporation for 20 min, vacuum fractionate, collect the distillate, and obtain triethylene glycol monomethyl ether amine; Step S2: Add 3.5 mL of triethylene glycol monomethyl etheramine, 0.55 g of tris(dibenzylacetone)dipalladium, 3.8 g of sodium tert-butoxide, 0.5 g of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 90 mL of toluene to a three-necked flask equipped with a stirrer and thermometer. Perform a "freezing-vacuuming-thawing" cycle three times. Add 6 g of [unspecified substance] under nitrogen protection at 25°C. 4-Bromo-2-fluoro-1-iodobenzene was stirred at 50℃ and 300 r / min for 22 h, cooled to 25℃, and quenched in a beaker containing 100 mL of 26% ammonium chloride solution. The mixture was separated using a separatory funnel, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried for 13 min with 8 g of anhydrous magnesium sulfate, and concentrated by evaporation at 33℃ for 20 min in a rotary evaporator. 750 mL of an eluent consisting of a mixture of petroleum ether and ethyl acetate in a volume ratio of 8:1 was added, and the mixture was purified by alumina column chromatography to obtain the aniline derivative. Step S3: Under 0℃ ice bath and nitrogen protection, 13 mL of ethyl magnesium bromide, 4 g of aniline derivative and 18 mL of tetrahydrofuran were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred for 13 min, heated to 30℃ and vacuum rotary evaporated for 1.5 h. 10 mg of ferrous chloride, 2 mL of 1,2-dibromoethane and 30 mL of toluene were added. The mixture was stirred at 450 r / min for 12 h under nitrogen protection and 100℃. After the reaction was completed, the mixture was naturally cooled to 25℃, quenched with 50 mL of deionized water, extracted three times with 90 mL of dichloromethane, and the organic phase was washed twice with 26% sodium chloride solution. 8 g of anhydrous magnesium sulfate was added and dried for 13 min. The mixture was evaporated and concentrated at 23℃ for 10 min to obtain the intermediate. Step S4: Add 0.15g of 5,10-dihydrophenazine, 0.45g of the intermediate, 0.25g of sodium tert-butoxide, and 25mL of xylene to a three-necked flask equipped with a stirrer and thermometer, and sonicate to degas for 8 minutes to obtain the first solution; add 13mg of palladium acetate and 45mg... 2-Bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl and 15 mL xylene were mixed and stirred at 25 °C for 8 min to obtain a second solution. Under nitrogen protection, the second solution was added to the first solution, and the "freezing-vacuuming-thawing" cycle was performed three times. The mixture was stirred at 120 °C at 600 r / min for 24 h, and stirred at 140 °C for 12 h. The temperature was lowered to 120 °C, 0.8 mL of bromobenzene was added, and the mixture was stirred for 5.5 h. The mixture was then naturally cooled to 25 °C, and 200 mL of a mixed solvent of methanol and acetone in a volume ratio of 1:1 was added. The mixture was stirred for 30 min, filtered, and the filter cake was washed three times with o-xylene, tetrahydrofuran, and acetonitrile in sequence. The cake was then transferred to a vacuum drying oven at 60 °C and dried for 24 h to obtain the cathode material. Step S5: Add 12g zirconium nitrate pentahydrate, 8mL tetraethyl silicate, 3.5g ammonium dihydrogen phosphate, 4.5g sodium nitrate, and 125mL of 75% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Add 16g citric acid and stir magnetically at 300r / min for 7 hours. Place the flask in an 80℃ water bath and continue stirring at 200r / min for 3.5 hours. Transfer the flask to a 120℃ drying oven and dry for 11 hours. h, placed in a muffle furnace, heated to 350℃ at a rate of 3℃ / min under air atmosphere and sintered for 4h, added to a mortar and ground, heated to 900℃ at a rate of 5℃ / min and sintered for 12h, naturally cooled to 25℃, added to a planetary ball mill with a ball-to-material ratio of 10:1, added 90mL of anhydrous ethanol, ball milled at 350r / min for 7h, dried at 80℃ for 5.5h, and then sieved through a 400-mesh sieve to obtain crystalline powder; Step S6: Add 5.5g of crystalline powder and 100mL of 90% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Sonicate for 30min, place in an oil bath at 75℃, stir at 400r / min for 30min, adjust the pH to 11 with ammonia, and continue stirring and activating for 1h to obtain a suspension. Add 5.5mL of methoxy polyethylene glycol silane P001012-2K and 10mL of anhydrous ethanol to a beaker and mix and stir for 30min. Add the above suspension, stir and react at 75℃ and 400r / min for 7h, transfer to a dialysis bag with a molecular weight cutoff of 11000 and dialyze for 72h. Freeze-dry at -50℃ for 36h to obtain the functional filler. Step S7: Add 1.2g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, 0.6g of sodium perchlorate, and 20mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Stir magnetically at 500r / min for 7 hours at 50℃, allow to stand for 30 minutes to degas, and then cast into a film using a casting machine. Transfer the film to a 60℃ forced-air drying oven and dry for 6 hours to obtain a supported film. Mix 0.23g of functional filler and 10mL of acetonitrile and ultrasonically disperse for 1 minute. h, add 0.5g of sodium bis(trifluoromethanesulfonyl)imide, and stir magnetically at 400r / min for 2.5h. Add 0.5g of polyethylene oxide P432437 and 0.6g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, and stir at 450r / min for 60h. Let stand to degas for 30min, cast the film on the surface of the support membrane, let stand at 25℃ for 12h, and transfer to a vacuum drying oven at 55℃ for 36h to obtain a solid electrolyte membrane. Step S8: Weigh out 75 parts of positive electrode material, 12 parts of conductive carbon black ENSACO 250G, 8 parts of polyvinylidene fluoride HSV900, 90 parts of N-methyl-2-pyrrolidone, 8 parts of copper foil, 180 parts of solid electrolyte membrane, 140 parts of sodium sheet and 40 parts of aluminum foil according to the following weight. Step S9: Add the positive electrode material, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto a copper foil, dry it in a vacuum at 60°C for 12 h, and then cut it into discs as positive electrode sheets; punch the solid electrolyte membrane into discs, place them on a hot press, and hot press them at 60°C and 5 MPa for 3 min; place the sodium sheet on an aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it with a constant pressure of 650 MPa, and let it stand at 25°C for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0033] Example 3:

[0034] This embodiment describes a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, including the following steps: Step S1: Add 50 mL of triethylene glycol monomethyl ether and 5 g of Raney nickel to the reaction vessel, purge the air in the vessel with nitrogen, purge with ammonia until saturated, purge with hydrogen at 3 MPa, heat to 205 °C, mix and stir for 35 h, cool naturally to 25 °C, adjust the pH to 3 with 2 mol / L hydrochloric acid solution, distill under reduced pressure, add 100 mL of 50% sodium hydroxide solution, mix and stir for 30 min, extract three times with dichloromethane, combine the organic phases, add 15 g of anhydrous magnesium sulfate and dry for 15 min, filter, concentrate by rotary evaporation for 30 min, vacuum fractionate, collect the distillate, and obtain triethylene glycol monomethyl ether amine; Step S2: Add 4 mL of triethylene glycol monomethyl etheramine, 0.6 g of tris(dibenzylacetone)dipalladium, 4 g of sodium tert-butoxide, 0.6 g of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 100 mL of toluene to a three-necked flask equipped with a stirrer and thermometer. Perform a "freezing-vacuuming-thawing" cycle three times. Add 7 g of [unspecified substance] under nitrogen protection at 25°C. 4-Bromo-2-fluoro-1-iodobenzene was stirred at 50℃ and 300 r / min for 24 h, cooled to 25℃, and quenched in a beaker containing 100 mL of 26% ammonium chloride solution. The mixture was separated using a separatory funnel, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried for 15 min with 10 g of anhydrous magnesium sulfate, and concentrated by evaporation at 35℃ for 30 min in a rotary evaporator. 1000 mL of an eluent consisting of a 10:1 volume ratio of petroleum ether and ethyl acetate was added, and the mixture was purified by alumina column chromatography to obtain the aniline derivative. Step S3: Under 0℃ ice bath and nitrogen protection, 15 mL of ethyl magnesium bromide, 5 g of aniline derivative and 20 mL of tetrahydrofuran were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred for 15 min, heated to 35℃ and vacuum rotary evaporated for 2 h. 15 mg of ferrous chloride, 3 mL of 1,2-dibromoethane and 30 mL of toluene were added. The mixture was stirred at 500 r / min for 12 h under nitrogen protection and 100℃. After the reaction was completed, the mixture was naturally cooled to 25℃, quenched with 50 mL of deionized water, extracted three times with 90 mL of dichloromethane, and the organic phase was washed twice with 26% sodium chloride solution. 10 g of anhydrous magnesium sulfate was added and dried for 15 min. The mixture was then evaporated and concentrated at 25℃ for 15 min to obtain the intermediate. Step S4: Add 0.2g of 5,10-dihydrophenazine, 0.5g of the intermediate, 0.3g of sodium tert-butoxide, and 25mL of xylene to a three-necked flask equipped with a stirrer and thermometer, and sonicate to degas for 10min to obtain the first solution; add 15mg of palladium acetate and 50mg... 2-Bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl and 15 mL xylene were mixed and stirred at 25 °C for 10 min to obtain a second solution. Under nitrogen protection, the second solution was added to the first solution, and the "freezing-vacuuming-thawing" cycle was performed three times. The mixture was stirred at 120 °C at 600 r / min for 24 h, and stirred at 140 °C for 12 h. The temperature was lowered to 120 °C, 1 mL of bromobenzene was added, and the mixture was stirred for 6 h. The mixture was then naturally cooled to 25 °C, and 200 mL of a mixed solvent of methanol and acetone in a volume ratio of 1:1 was added. The mixture was stirred for 30 min, filtered, and the filter cake was washed three times in sequence with o-xylene, tetrahydrofuran, and acetonitrile. The cake was then transferred to a vacuum drying oven at 60 °C and dried for 24 h to obtain the cathode material. Step S5: Add 13g zirconium nitrate pentahydrate, 10mL tetraethyl silicate, 4g ammonium dihydrogen phosphate, 5g sodium nitrate, and 125mL of 75% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Add 17g citric acid and stir magnetically at 300r / min for 8 hours. Place the flask in an 80℃ water bath and continue stirring at 200r / min for 4 hours. Transfer the flask to a 120℃ drying oven and dry for 12 hours. Placed in a muffle furnace, sintered at 350℃ for 4 hours in air atmosphere at a rate of 3℃ / min. Then, it was ground in a mortar and sintered at 900℃ for 12 hours at a rate of 5℃ / min. After natural cooling to 25℃, it was placed in a planetary ball mill with a ball-to-material ratio of 10:1. 100 mL of anhydrous ethanol was added, and the mixture was ball-milled at 350 r / min for 8 hours. After drying at 80℃ for 6 hours, the powder was sieved through a 400-mesh sieve to obtain crystalline powder. Step S6: Add 6g of crystalline powder and 100mL of 90% ethanol solution to a three-necked flask equipped with a stirrer and thermometer, sonicate for 30min, place in an oil bath at 75℃, stir at 400r / min for 30min, adjust the pH to 11 with ammonia, continue stirring and activating for 1h to obtain a suspension; add 6mL of methoxy polyethylene glycol silane P001012-2K and 10mL of anhydrous ethanol to a beaker and mix and stir for 30min, add the above suspension, stir and react at 75℃ and 400r / min for 8h, transfer to a dialysis bag with a molecular weight cutoff of 14000 and dialyze for 72h, freeze-dry at -50℃ for 48h to obtain the functional filler; Step S7: Add 1.6g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, 0.8g of sodium perchlorate, and 20mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Stir magnetically at 500r / min for 8 hours at 50℃, allow to stand for 30 minutes to degas, cast into a film using a casting machine, and transfer to a 60℃ forced-air drying oven for 6 hours to obtain a supported film; mix and ultrasonically disperse 0.3g of functional filler and 10mL of acetonitrile. 1 h, add 0.6 g of sodium bis(trifluoromethanesulfonyl)imide, stir magnetically at 400 r / min for 3 h, add 0.6 g of polyethylene oxide P432437 and 0.8 g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, stir at 600 r / min for 72 h, let stand to degas for 30 min, cast on the surface of the support membrane to form a film, let stand at 25 °C for 12 h, transfer to a vacuum drying oven at 60 °C and dry for 48 h to obtain a solid electrolyte membrane; Step S8: Weigh out 80 parts of positive electrode material, 15 parts of conductive carbon black ENSACO 250G, 10 parts of polyvinylidene fluoride HSV900, 100 parts of N-methyl-2-pyrrolidone, 10 parts of copper foil, 200 parts of solid electrolyte membrane, 150 parts of sodium sheet and 50 parts of aluminum foil according to the following weight. Step S9: Add the positive electrode material, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto a copper foil, dry it in a vacuum at 60°C for 12 h, and then cut it into discs as positive electrode sheets; punch the solid electrolyte membrane into discs, place them on a hot press, and hot press them at 60°C and 5 MPa for 3 min; place the sodium sheet on an aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it with a constant pressure of 750 MPa, and let it stand at 25°C for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0035] Comparative Example 1: This comparative example illustrates a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, comprising the following steps: Step S1: Weigh out 75 parts sodium vanadium phosphate, 12 parts conductive carbon black ENSACO 250G, 8 parts polyvinylidene fluoride HSV900, 90 parts N-methyl-2-pyrrolidone, 8 parts copper foil, 180 parts Na3PS4, 140 parts sodium flakes and 40 parts aluminum foil according to the following weight. Step S2: Add sodium vanadium phosphate, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto copper foil, dry it in a vacuum at 60℃ for 12 h, and then cut it into discs as positive electrode sheets; punch Na3PS4 into discs, place them on a hot press, and hot press them at 60℃ and 5MPa for 3 min; place the sodium sheet on aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack them from bottom to top in the order of positive electrode sheet-solid electrolyte membrane-negative electrode sheet, press and seal them with a constant pressure of 650MPa, and let them stand at 25℃ for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0036] Comparative Example 2: This comparative example illustrates a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, comprising the following steps: Step S1: Add 45 mL of triethylene glycol monomethyl ether and 4.5 g of Raney nickel to the reaction vessel, purge the air in the vessel with nitrogen, purge with ammonia until saturated, purge with 2 MPa of hydrogen, heat to 205 °C, mix and stir for 30 h, cool naturally to 25 °C, adjust the pH to 3 with 2 mol / L hydrochloric acid solution, distill under reduced pressure, add 90 mL of 50% sodium hydroxide solution, mix and stir for 30 min, extract three times with dichloromethane, combine the organic phases, add 13 g of anhydrous magnesium sulfate and dry for 13 min, filter, concentrate by rotary evaporation for 20 min, vacuum fractionate, collect the distillate, and obtain triethylene glycol monomethyl ether amine; Step S2: Add 3.5 mL of triethylene glycol monomethyl etheramine, 0.55 g of tris(dibenzylacetone)dipalladium, 3.8 g of sodium tert-butoxide, 0.5 g of 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 90 mL of toluene to a three-necked flask equipped with a stirrer and thermometer. Perform a "freezing-vacuuming-thawing" cycle three times. Add 6 g of [unspecified substance] under nitrogen protection at 25°C. 4-Bromo-2-fluoro-1-iodobenzene was stirred at 50℃ and 300 r / min for 22 h, cooled to 25℃, and quenched in a beaker containing 100 mL of 26% ammonium chloride solution. The mixture was separated using a separatory funnel, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried for 13 min with 8 g of anhydrous magnesium sulfate, and concentrated by evaporation at 33℃ for 20 min in a rotary evaporator. 750 mL of an eluent consisting of a mixture of petroleum ether and ethyl acetate in a volume ratio of 8:1 was added, and the mixture was purified by alumina column chromatography to obtain the aniline derivative. Step S3: Under 0℃ ice bath and nitrogen protection, 13 mL of ethyl magnesium bromide, 4 g of aniline derivative and 18 mL of tetrahydrofuran were added to a three-necked flask equipped with a stirrer and thermometer. The mixture was stirred for 13 min, heated to 30℃ and vacuum rotary evaporated for 1.5 h. 10 mg of ferrous chloride, 2 mL of 1,2-dibromoethane and 30 mL of toluene were added. The mixture was stirred at 450 r / min for 12 h under nitrogen protection and 100℃. After the reaction was completed, the mixture was naturally cooled to 25℃, quenched with 50 mL of deionized water, extracted three times with 90 mL of dichloromethane, and the organic phase was washed twice with 26% sodium chloride solution. 8 g of anhydrous magnesium sulfate was added and dried for 13 min. The mixture was evaporated and concentrated at 23℃ for 10 min to obtain the intermediate. Step S4: Add 0.15g of 5,10-dihydrophenazine, 0.45g of the intermediate, 0.25g of sodium tert-butoxide, and 25mL of xylene to a three-necked flask equipped with a stirrer and thermometer, and sonicate to degas for 8 minutes to obtain the first solution; add 13mg of palladium acetate and 45mg... 2-Bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl and 15 mL xylene were mixed and stirred at 25 °C for 8 min to obtain a second solution. Under nitrogen protection, the second solution was added to the first solution, and the "freezing-vacuuming-thawing" cycle was performed three times. The mixture was stirred at 120 °C at 600 r / min for 24 h, and stirred at 140 °C for 12 h. The temperature was lowered to 120 °C, 0.8 mL of bromobenzene was added, and the mixture was stirred for 5.5 h. The mixture was then naturally cooled to 25 °C, and 200 mL of a mixed solvent of methanol and acetone in a volume ratio of 1:1 was added. The mixture was stirred for 30 min, filtered, and the filter cake was washed three times with o-xylene, tetrahydrofuran, and acetonitrile in sequence. The cake was then transferred to a vacuum drying oven at 60 °C and dried for 24 h to obtain the cathode material. Step S5: Weigh out 75 parts of positive electrode material, 12 parts of conductive carbon black ENSACO 250G, 8 parts of polyvinylidene fluoride HSV900, 90 parts of N-methyl-2-pyrrolidone, 8 parts of copper foil, 180 parts of Na3PS4, 140 parts of sodium sheet and 40 parts of aluminum foil according to the following weight. Step S6: Add the positive electrode material, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto copper foil, dry it in a vacuum at 60°C for 12 h, and then cut it into discs as positive electrode sheets; punch Na3PS4 into discs, place them on a hot press, and hot press them at 60°C and 5 MPa for 3 min; place the sodium sheet on aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it with a constant pressure of 650 MPa, and let it stand at 25°C for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0037] Comparative Example 3: This comparative example illustrates a method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte, comprising the following steps: Step S1: Add 12g zirconium nitrate pentahydrate, 8mL tetraethyl silicate, 3.5g ammonium dihydrogen phosphate, 4.5g sodium nitrate, and 125mL of 75% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Add 16g citric acid and stir magnetically at 300r / min for 7 hours. Place the flask in an 80℃ water bath and continue stirring at 200r / min for 3.5 hours. Transfer the flask to a 120℃ drying oven and dry for 11 hours. h, placed in a muffle furnace, heated to 350℃ at a rate of 3℃ / min under air atmosphere and sintered for 4h, added to a mortar and ground, heated to 900℃ at a rate of 5℃ / min and sintered for 12h, naturally cooled to 25℃, added to a planetary ball mill with a ball-to-material ratio of 10:1, added 90mL of anhydrous ethanol, ball milled at 350r / min for 7h, dried at 80℃ for 5.5h, and then sieved through a 400-mesh sieve to obtain crystalline powder; Step S2: Add 5.5g of crystalline powder and 100mL of 90% ethanol solution to a three-necked flask equipped with a stirrer and thermometer. Sonicate the mixture for 30min, place it in an oil bath at 75℃, and stir at 400r / min for 30min. Adjust the pH to 11 with ammonia and continue stirring for 1h to obtain a suspension. Add 5.5mL of methoxy polyethylene glycol silane P001012-2K and 10mL of anhydrous ethanol to a beaker and mix and stir for 30min. Add the above suspension and stir the mixture at 75℃ and 400r / min for 7h. Transfer the mixture to a dialysis bag with a molecular weight cutoff of 11000 and dialyze for 72h. Freeze-dry the mixture at -50℃ for 36h to obtain the functional filler. Step S3: Add 1.2g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, 0.6g of sodium perchlorate, and 20mL of N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Stir magnetically at 500r / min for 7 hours at 50℃, allow to stand for 30 minutes to degas, and then cast into a film using a casting machine. Transfer the film to a 60℃ forced-air drying oven and dry for 6 hours to obtain a supported film. Mix 0.23g of functional filler and 10mL of acetonitrile and ultrasonically disperse for 1 minute. h, add 0.5g of sodium bis(trifluoromethanesulfonyl)imide, and stir magnetically at 400r / min for 2.5h. Add 0.5g of polyethylene oxide P432437 and 0.6g of polyvinylidene fluoride-hexafluoropropylene copolymer lnb-1003, and stir at 450r / min for 60h. Let stand to degas for 30min, cast the film on the surface of the support membrane, let stand at 25℃ for 12h, and transfer to a vacuum drying oven at 55℃ for 36h to obtain a solid electrolyte membrane. Step S4: Weigh out 75 parts sodium vanadium phosphate, 12 parts conductive carbon black ENSACO 250G, 8 parts polyvinylidene fluoride HSV900, 90 parts N-methyl-2-pyrrolidone, 8 parts copper foil, 180 parts solid electrolyte membrane, 140 parts sodium sheet and 40 parts aluminum foil according to the following weight. Step S5: Add sodium vanadium phosphate, conductive carbon black ENSACO 250G, polyvinylidene fluoride HSV900, and N-methyl-2-pyrrolidone to a centrifugal mixer and stir for 30 min to obtain a positive electrode slurry; coat the positive electrode slurry onto copper foil, dry it in a vacuum at 60℃ for 12 h, and then cut it into discs as positive electrode sheets; punch the solid electrolyte membrane into discs, place them on a hot press, and hot press them at 60℃ and 5MPa for 3 min; place the sodium sheet on aluminum foil, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it with a constant pressure of 650MPa, and let it stand at 25℃ for 24 h to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

[0038] The solid-state energy storage batteries based on high-performance solid-state electrolytes prepared in Examples 1-3 and Comparative Examples 1-3 were tested for cycle stability (1C rate, capacity retention after 1000 cycles) according to GB / T 36276-2023 standard. EIS (10mV, 7MHz-100MHz) was tested at room temperature. The ionic conductivity of the electrolyte was calculated using the formula σ=L / (R*S): L is the electrolyte thickness, R is the measured electrolyte bulk impedance, and S is the electrolyte area. The conductivity of the prepared solid-state electrolyte was calculated from the actual measured impedance spectrum and the electrolyte thickness and area. The test results are as follows: Figure 1-2 As shown: Comparing Examples 1-3 with Comparative Examples 1-3: The reactant ratios and times gradually increased in Examples 1-3, altering monomer conversion and product purity. Example 2 achieved the optimal ratio, resulting in a more complete reaction and fewer impurities. Bromobenzene was used to terminate polymer chain growth; in Example 1, the amount was insufficient, leading to uncapped chain ends and a wider molecular weight distribution. In Example 3, the amount was excessive, introducing small molecule impurities and affecting the integrity of ion transport channels. In Example 1, the amount of methoxy polyethylene glycol silane was too low, resulting in insufficient grafting rate and slightly poor filler dispersibility. In Example 3, the amount was too high, potentially leading to excessive entanglement of methoxy polyethylene glycol silane chains. The amount used in Example 2 represented the optimal grafting density and conformation, achieving optimal dispersion and interfacial coupling in the polymer matrix, resulting in the best performance. Comparing Example 2 with Comparative Example 1 shows that: Comparative Example 1 used inorganic sodium vanadium phosphate as the positive electrode material and sulfide Na3PS4 as the electrolyte. Both the inorganic positive electrode and the inorganic electrolyte were rigid, with solid-solid point contact. The surface impedance is high and it is easy to peel off due to volume changes during cycling. In Example 2, the organic positive electrode is relatively soft and can form a tight, low-stress interface with the equally soft polyethylene oxide electrolyte. Comparing Example 2 with Comparative Example 2, it can be seen that: Comparative Example 2 uses a traditional sulfide electrolyte. It is difficult for the soft organic polymer positive electrode and the hard sulfide ceramic electrolyte to form a tight contact, resulting in a huge initial interface impedance. The ether oxygen chain of the positive electrode is completely different from the chemical environment of the sulfide, and it is impossible to form a molecular-level fusion interface. During charging and discharging, continuous chemical side reactions and charge accumulation are likely to occur at the interface, which accelerates the performance degradation. Comparing Example 2 with Comparative Example 3, it can be seen that: Comparative Example 3 uses a traditional inorganic positive electrode, sodium vanadium phosphate. Inorganic materials such as sodium vanadium phosphate have a large lattice volume expansion / contraction during charging and discharging, which will generate huge local stress. The electrolyte is not enough to completely buffer the drastic volume changes of the inorganic positive electrode. Repeated stress will cause the positive electrode particles to break and the interface with the electrolyte to fail, resulting in a decrease in performance.

[0039] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0040] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A solid-state energy storage battery based on a high-performance solid-state electrolyte, characterized in that, Includes the following components by weight: 70-80 parts of positive electrode material, 8-15 parts of conductive carbon black, 5-10 parts of polyvinylidene fluoride, 5-10 parts of positive electrode current collector, 150-200 parts of solid electrolyte membrane, 130-150 parts of negative electrode material, and 30-50 parts of negative electrode current collector. The positive electrode material is prepared by the following steps: Step a1: Triethylene glycol monomethyl ether and Raney nickel were added to a reaction vessel, nitrogen was introduced to replace the air in the vessel, ammonia was introduced until saturation, hydrogen was introduced, the reaction was heated and stirred, cooled, pH was adjusted with hydrochloric acid solution, vacuum distillation was performed, sodium hydroxide solution was added, the mixture was stirred, extracted, anhydrous magnesium sulfate was added to dry, filtered, concentrated by rotary evaporation, vacuum fractionation was performed, and the fraction was collected to obtain triethylene glycol monomethyl ether amine; Step a2: Triethylene glycol monomethyl etheramine, tris(dibenzylacetone)dipalladium, sodium tert-butoxide, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and toluene were mixed and subjected to a "freeze-vacuum-thaw" cycle three times. 4-bromo-2-fluoro-1-iodobenzene was added, the reaction was stirred, cooled, and the mixture was poured into a beaker containing ammonium chloride solution for quenching. The mixture was then separated, extracted, and the organic phases were combined. Anhydrous magnesium sulfate was added for drying, the mixture was evaporated and concentrated, eluent was added, and the mixture was purified by chromatography to obtain the aniline derivative. Step a3: Mix and stir ethyl magnesium bromide, aniline derivative and tetrahydrofuran, vacuum rotary evaporate, add ferrous chloride, 1,2-dibromoethane and toluene, stir the reaction, cool, quench with deionized water, extract with dichloromethane, wash the organic phase with sodium chloride solution, dry with anhydrous magnesium sulfate, evaporate and concentrate to obtain intermediate; Step a4: Mix 5,10-dihydrophenazine, the intermediate, sodium tert-butoxide, and the first portion of xylene and degas using ultrasonication to obtain a first solution; mix palladium acetate, 2-bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl, and the second portion of xylene and stir to obtain a second solution; add the second solution to the first solution and perform a "freeze-vacuum-thaw" cycle three times, stirring the reaction; add bromobenzene, stir the reaction, cool, add the mixed solvent, mix and stir, filter, wash the filter cake, and dry to obtain the positive electrode material.

2. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, The conductive carbon black is ENSACO 250G; the polyvinylidene fluoride is HSV900; the positive electrode current collector is copper foil; the negative electrode material is sodium sheet; and the negative electrode current collector is aluminum foil.

3. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, In step a1, the ratio of triethylene glycol monomethyl ether, Raney nickel, sodium hydroxide solution, and anhydrous magnesium sulfate is 40-50 mL: 4-5 g: 80-100 mL: 10-15 g; the concentration of the hydrochloric acid solution is 2 mol / L; and the mass fraction of the sodium hydroxide solution is 50%.

4. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, In step a2, the ratio of triethylene glycol monomethyl etheramine, tris(dibenzylacetone)dipalladium, sodium tert-butoxide, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, toluene, 4-bromo-2-fluoro-1-iodobenzene, ammonium chloride solution, anhydrous magnesium sulfate, and eluent is 3-4 mL : 0.5-0.6 g : 3.5-4 g : 0.4-0.6 g : 80-100 mL : 5-7 g : 100 mL : 5-10 g : 500-1000 mL; the mass fraction of the ammonium chloride solution is 26%; and the eluent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 5-10:

1.

5. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, The ratio of ethyl magnesium bromide, aniline derivative, tetrahydrofuran, ferrous chloride, 1,2-dibromoethane, toluene, deionized water, dichloromethane, and anhydrous magnesium sulfate in step a3 is 10-15 mL: 3-5 g: 15-20 mL: 5-15 mg: 1-3 mL: 30 mL: 50 mL: 90 mL: 5-10 g; the mass fraction of the sodium chloride solution is 26%; the total amount of 5,10-dihydrophenazine, intermediate, sodium tert-butoxide, xylene, and acetic acid in step a4 is... The ratio of palladium acid, 2-bicyclohexylphosphine-2,4',6'-triisopropylbiphenyl, bromobenzene, and the mixed solvent is 0.1-0.2g:0.4-0.5g:0.2-0.3g:40mL:10-15mg:40-50mg:0.5-1mL:200mL; the first part of xylene accounts for 5 / 8 of the total xylene; the second part of xylene accounts for 3 / 8 of the total xylene; the mixed solvent is prepared by mixing methanol and acetone in a volume ratio of 1:

1.

6. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, The solid electrolyte membrane is prepared by the following steps: Step b1: Zirconium nitrate pentahydrate, tetraethyl silicate, ammonium dihydrogen phosphate, sodium nitrate, ethanol solution, and complexing agent are magnetically stirred, placed in a water bath and stirred continuously, dried, sintered, ground, heated and sintered again, cooled, added to a ball mill with a ball-to-material ratio of 10:1, anhydrous ethanol is added, ball milling is performed, dried, ground and then sieved through a sieve to obtain crystalline powder; Step b2: The crystalline powder and ethanol solution are ultrasonically dispersed, stirred in an oil bath, and the pH is adjusted to 11 with ammonia water. After stirring and activation, a suspension is obtained. The methoxy polyethylene glycol silane and anhydrous ethanol are mixed and stirred, added to the above suspension, stirred and reacted, dialyzed, and freeze-dried to obtain the functional filler. Step b3: The first part of polyvinylidene fluoride-hexafluoropropylene copolymer, sodium perchlorate and N,N-dimethylformamide are magnetically stirred, allowed to stand to remove bubbles, cast into a film using a casting machine, and dried to obtain a support film; the functional filler and acetonitrile are mixed and ultrasonically dispersed, bis(trifluoromethanesulfonyl)imide sodium is added, magnetically stirred, polyethylene oxide and the second part of polyvinylidene fluoride-hexafluoropropylene copolymer are added, stirred, allowed to stand to remove bubbles, cast into a film on the surface of the support film, allowed to stand, and dried to obtain a solid electrolyte membrane.

7. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 6, characterized in that, In step b1, the ratio of zirconium nitrate pentahydrate, tetraethyl silicate, ammonium dihydrogen phosphate, sodium nitrate, ethanol solution, complexing agent, and anhydrous ethanol is 10-13g: 5-10mL: 3-4g: 4-5g: 125mL: 15-17g: 80-100mL; the ethanol solution has a mass fraction of 75%; the complexing agent is citric acid. In step b2, the ratio of crystalline powder, ethanol solution, methoxy polyethylene glycol silane, and anhydrous ethanol is 5-6g: 100mL: 5-6mL: 10mL; the ethanol solution has a mass fraction of 90%; the methoxy polyethylene glycol silane is of type P001012 with a molecular weight of 2K.

8. The solid-state energy storage battery based on a high-performance solid-state electrolyte according to claim 1, characterized in that, In step b3, the ratio of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer, sodium perchlorate, N,N-dimethylformamide, functional filler, acetonitrile, sodium bis(trifluoromethanesulfonyl)imide, and polyethylene oxide is 1.2-2.4g:0.4-0.8g:20mL:0.15-0.3g:10mL:0.4-0.6g:0.4-0.6g; the polyvinylidene fluoride-hexafluoropropylene copolymer is produced by Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., with the product number lnb-1003; the polyethylene oxide is produced by Aladdin brand, with the product number P432437; the first part of polyvinylidene fluoride-hexafluoropropylene copolymer accounts for 2 / 3 of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer; the second part of polyvinylidene fluoride-hexafluoropropylene copolymer accounts for 1 / 3 of the total amount of polyvinylidene fluoride-hexafluoropropylene copolymer.

9. A method for preparing a solid-state energy storage battery based on a high-performance solid-state electrolyte as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Weigh out the following components by weight: 70-80 parts of positive electrode material, 8-15 parts of conductive carbon black, 5-10 parts of polyvinylidene fluoride, 80-100 parts of N-methyl-2-pyrrolidone, 5-10 parts of positive electrode current collector, 150-200 parts of solid electrolyte membrane, 130-150 parts of negative electrode material, and 30-50 parts of negative electrode current collector. Step 2: Mix and stir the positive electrode material, conductive carbon black, polyvinylidene fluoride, and N-methyl-2-pyrrolidone to obtain a positive electrode slurry; coat the positive electrode slurry onto the positive electrode current collector, dry it, and cut it into discs as positive electrode sheets; punch the solid electrolyte membrane into discs and hot press it on a hot press; place the negative electrode material on the negative electrode current collector, roll it with a roller press, and punch it into discs to obtain a negative electrode sheet; stack the positive electrode sheet-solid electrolyte membrane-negative electrode sheet from bottom to top, press and seal it, and let it stand to obtain a solid-state energy storage battery based on a high-performance solid electrolyte.

10. An application of a solid-state energy storage battery based on a high-performance solid-state electrolyte as described in any one of claims 1-8 in electric vehicles, drones, and portable electronic devices.

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