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CN-122025744-A - Diaphragm-free all-solid-state sodium ion energy storage battery and preparation method thereof

CN122025744ACN 122025744 ACN122025744 ACN 122025744ACN-122025744-A

Abstract

The invention relates to the field of sodium ion energy storage batteries, in particular to a diaphragm-free all-solid-state sodium ion energy storage battery and a preparation method thereof, which are used for solving the problems of low ionic conductivity of solid electrolyte, poor compatibility with an electrode interface and poor battery cycling stability caused by a positive electrode material; placing a negative electrode plate in a negative electrode shell, spreading a composite electrolyte membrane on the negative electrode plate, placing a positive electrode plate in the center of the composite electrolyte membrane, sequentially placing a stainless steel gasket and a wavy elastic sheet, covering the positive electrode shell, sealing by a button cell sealing machine, and standing to obtain a diaphragm-free all-solid-state sodium ion energy storage battery; the composite electrolyte membrane has high ionic conductivity and tensile strength, and the assembled battery has excellent multiplying power performance and cycle stability.

Inventors

  • ZOU WEIMIN
  • ZOU JIAYI
  • CAI HONGFU
  • GUAN GUOZHI
  • CHEN KEJIAN

Assignees

  • 江苏传艺科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260226

Claims (10)

  1. 1. A non-membrane all-solid-state sodium ion energy storage battery comprising: composite electrolyte membrane, positive electrode sheet and negative electrode sheet; Wherein the negative electrode sheet is a metal sodium sheet; wherein, the composite electrolyte membrane is prepared by the following steps: Step a1, mixing tetraethoxysilane and absolute ethyl alcohol, stirring for reaction, regulating pH, continuing stirring to form silica sol, dissolving sodium nitrate, zirconium oxychloride and ammonium dihydrogen phosphate in deionized water, stirring to obtain a mixed salt solution, dropwise adding the mixed salt solution into the silica sol, continuing stirring, standing, drying, grinding and sieving, sintering, cooling and grinding to obtain nano-grade NZSP powder; step a2, adding nano-grade NZSP powder into absolute ethyl alcohol for ultrasonic dispersion, dripping gamma-aminopropyl triethoxysilane, stirring for reaction, centrifuging, discarding supernatant, washing, drying and grinding to obtain amination modified NZSP; Step a3, mixing N-methylpyrrolidone, bisphenol A type diether dianhydride and 4,4' -diaminodiphenyl ether, stirring for reaction, then adding propylene oxide, continuously stirring, adding benzoxazine resin, continuously stirring, standing and defoaming to obtain a polymer solid electrolyte precursor solution; Step a4, adding a polymer solid electrolyte precursor solution into a three-neck flask, adding bis (trifluoromethyl sulfonyl) sodium imide, stirring for reaction, adding amination modification NZSP, stirring, performing ultrasonic dispersion, continuing stirring, standing and defoaming to obtain an organic-inorganic composite electrolyte solution; And a5, immersing the quartz plate into a dilute hydrochloric acid solution for ultrasonic cleaning, immersing the quartz plate into absolute ethyl alcohol for ultrasonic cleaning, drying, pouring an organic-inorganic composite electrolyte solution at one end of the quartz plate, pushing a scraper, carrying out sectional thermal crosslinking and solidification, cooling, tearing off a film, cutting, and then carrying out vacuum drying to obtain the composite electrolyte membrane.
  2. 2. The non-membrane all-solid-state sodium ion energy storage battery according to claim 1, wherein the dosage ratio of the ethyl orthosilicate, the absolute ethyl alcohol, the sodium nitrate, the zirconium oxychloride, the ammonium dihydrogen phosphate and the deionized water in the step a1 is 2-4g:20-40mL:1.82-3.64g:4.38-8.76g:0.85-1.70g:10-20mL.
  3. 3. The non-membrane all-solid-state sodium ion energy storage battery according to claim 1, wherein the dosage ratio of the nano-grade NZSP powder, the absolute ethyl alcohol and the gamma-aminopropyl triethoxysilane in the step a2 is 5-10g:100-200ml:0.15-0.30g.
  4. 4. The non-membrane all-solid-state sodium ion energy storage battery according to claim 1, wherein the dosage ratio of the N-methylpyrrolidone, bisphenol a diether dianhydride, 4' -diaminodiphenyl ether, propylene oxide and benzoxazine resin in step a3 is 90-180ml:0.52-1.04g:0.22-0.44g:0.014-0.028ml:4.66-9.32g.
  5. 5. The non-membrane all-solid-state sodium ion energy storage battery according to claim 1, wherein the polymer solid electrolyte precursor solution, sodium bis (trifluoromethylsulfonyl) imide, and amination modification NZSP in step a4 are used in an amount ratio of 98-137ml:5-7g:10-14g.
  6. 6. The diaphragm-free all-solid-state sodium ion energy storage battery according to claim 1, wherein the dosage ratio of the dilute hydrochloric acid solution, the absolute ethyl alcohol and the organic-inorganic composite electrolyte solution in the step a5 is 1500-2000mL:1500-2000mL:30-40mL, the mass fraction of the dilute hydrochloric acid solution is 5%, and the size of the quartz plate is 20cm multiplied by 20cm.
  7. 7. The non-membrane all-solid-state sodium ion energy storage battery according to claim 1, wherein the positive plate is prepared by the following steps: Step b1, placing sodium carbonate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, ferric nitrate nonahydrate, manganese nitrate and ammonium fluoride in an agate mortar, adding absolute ethyl alcohol, grinding, sintering, and cooling to obtain co-doped sodium nickel iron manganate powder; step b2, adding co-doped sodium ferronickel manganate powder into absolute ethyl alcohol for ultrasonic dispersion, dropwise adding the mixed solution, stirring, standing, drying, grinding, heating, and cooling to obtain a coated modified anode material; and b3, adding polyvinylidene fluoride into N-methyl pyrrolidone, stirring, adding a coated modified anode material and conductive carbon black, stirring, performing ultrasonic dispersion to obtain anode slurry, coating the anode slurry on the cleaned aluminum foil, standing, drying, rolling a piezoelectric plate, and cutting to obtain the anode plate.
  8. 8. The diaphragm-free all-solid-state sodium ion energy storage battery according to claim 7, wherein the dosage ratio of sodium carbonate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, ferric nitrate nonahydrate, manganese nitrate, ammonium fluoride and absolute ethyl alcohol in step b1 is 2.92-5.84g, 5.63-11.26g, 0.12-0.24g, 8-16g, 3.89-7.78g, 0.11-0.22g, 5-10mL, the dosage ratio of the co-doped sodium nickel iron manganese oxide powder, absolute ethyl alcohol and mixed solution in step b2 is 10-12g, 50-60mL, 12.0-14.4mL, and the dosage ratio of the polyvinylidene fluoride, N-methylpyrrolidone, coated modified cathode material and conductive carbon black in step b3 is 0.5-0.7g, 10.0-16.8mL, 4.0-5.6g, 0.5-0.7g.
  9. 9. The diaphragm-free all-solid-state sodium ion energy storage battery according to claim 7, wherein the mixed solution in the step b2 is a solution formed by mixing a sodium nitrate solution and a diammonium hydrogen phosphate solution according to a volume ratio of 2:1, the concentration of the sodium nitrate solution is 0.1mol/L, the concentration of the diammonium hydrogen phosphate solution is 0.1mol/L, and the thickness of the aluminum foil in the step b3 is 10-20 μm.
  10. 10. A method for preparing the non-diaphragm all-solid-state sodium ion energy storage battery, which is characterized by comprising the following steps of: Placing a negative plate in a negative shell, tiling a composite electrolyte membrane on the negative plate, then placing a positive plate in the center of the composite electrolyte membrane, sequentially placing a stainless steel gasket and a wavy spring plate, covering the positive shell, sealing, and standing to obtain the diaphragm-free all-solid-state sodium ion energy storage battery.

Description

Diaphragm-free all-solid-state sodium ion energy storage battery and preparation method thereof Technical Field The invention relates to the field of sodium ion energy storage batteries, in particular to a diaphragm-free all-solid-state sodium ion energy storage battery and a preparation method thereof. Background With the large-scale development and utilization of renewable energy sources, the demand for high-performance energy storage batteries is increasingly urgent. Sodium ion batteries become one of the important alternatives for lithium ion batteries because of the abundant sodium resource reserves and low cost. The traditional liquid sodium ion battery adopts organic electrolyte, has potential safety hazards of electrolyte leakage, inflammability, explosiveness and the like, and needs a diaphragm to isolate the anode and the cathode, thereby increasing the preparation cost and the process complexity of the battery. The solid electrolyte is used for replacing liquid electrolyte in the all-solid sodium ion battery, so that the safety problem of the electrolyte can be fundamentally solved, a diaphragm can be omitted, and the battery structure is simplified. However, the solid electrolyte of the existing all-solid-state sodium ion battery has the problems of low ionic conductivity, poor compatibility with an electrode interface and the like, and meanwhile, the anode material is easy to generate lattice distortion and dissolution of transition metal in the charge and discharge process, so that the battery has poor cycling stability. Therefore, the development of a solid electrolyte with high ionic conductivity, excellent interface compatibility and mechanical properties and a cathode material with high stability is a key for pushing the practical application of the diaphragm-free all-solid-state sodium ion battery. Disclosure of Invention In order to overcome the technical problems, the invention aims to provide a diaphragm-free all-solid-state sodium ion energy storage battery and a preparation method thereof. The aim of the invention can be achieved by the following technical scheme: In a first aspect, the present application provides a non-membrane all-solid sodium ion energy storage battery comprising: composite electrolyte membrane, positive electrode sheet and negative electrode sheet; Wherein the negative electrode sheet is a metal sodium sheet; wherein, the composite electrolyte membrane is prepared by the following steps: Adding tetraethoxysilane and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring and reacting for 20-30min under the condition that the temperature is 25-30 ℃ and the stirring speed is 300-400r/min, adjusting the pH value to 1-2 by using a nitric acid solution, continuously stirring for 60-70min to form silica sol, dissolving sodium nitrate, zirconium oxychloride and ammonium dihydrogen phosphate into deionized water, stirring for 15-20min to obtain a mixed salt solution, dropwise adding the mixed salt solution into the silica sol, continuously stirring for 2.2h, standing at room temperature for 24-25h, then placing into a vacuum drying box, firstly drying for 12-13h under the condition that the temperature is 55-60 ℃, then heating to 110-120 ℃ for 6h, grinding and sieving with a 200 mesh sieve, placing into an alumina crucible, placing into a muffle furnace, heating to 550 ℃ at the heating speed of 2 ℃ and the temperature of 550 ℃ for 3h, grinding again for 30-35min, continuously stirring for 2-35 h, standing at the room temperature for 24-25h, and cooling to obtain grinding powder at the temperature of NZSP ℃ and the nanometer grade; Adding nano-grade NZSP powder into absolute ethyl alcohol, performing ultrasonic dispersion for 30-35min under the condition of power of 200-250W, transferring into a three-neck flask, dripping gamma-aminopropyl triethoxysilane, stirring at the temperature of 55-60 ℃ and the stirring rate of 300-400r/min for 2-2.2h, centrifuging for 10-12min under the condition of the rotating speed of 8000r/min, discarding supernatant, washing for 3-5 times with isopropanol, transferring the precipitate into a vacuum drying oven, drying for 12-13h under the condition of the temperature of 75-80 ℃, and grinding to obtain amination modified NZSP; Step a3, adding N-methylpyrrolidone, bisphenol A type diether dianhydride and 4,4' -diaminodiphenyl ether into a three-neck flask provided with a stirrer, a thermometer, an air duct and a drying pipe, introducing nitrogen for protection, stirring and reacting for 12-13h under the condition that the temperature is 25-30 ℃ and the stirring speed is 300-350r/min, adding propylene oxide, continuing stirring for 8-9h, adding benzoxazine resin, continuing stirring for 4-5h, standing for 30-35min, and defoaming to obtain a polymer solid electrolyte precursor solution; Step a4, adding a polymer solid electrolyte precursor solution into