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CN-117452732-B - Bi-GO double-doped WO3Electrochromic film and preparation method and application thereof

CN117452732BCN 117452732 BCN117452732 BCN 117452732BCN-117452732-B

Abstract

The invention relates to a Bi-GO double-doped WO 3 electrochromic film, a preparation method and application thereof. The preparation method of the Bi-GO double-doped WO 3 electrochromic film comprises the following steps of dissolving tungsten acid in hydrogen peroxide solution to obtain peroxytungstic acid solution, adding bismuth-containing substances into the peroxytungstic acid solution, dissolving the bismuth-containing substances to obtain Bi-peroxytungstic acid solution, adding graphene-based material nano-sheet dispersion liquid into the Bi-peroxytungstic acid solution, stirring and heating to form uniform Bi-GO-peroxytungstic acid sol, spin-coating the Bi-GO-peroxytungstic acid sol on a conductive glass substrate, and roasting to obtain the Bi-GO-peroxytungstic acid film. The Bi-GO double-doped WO 3 electrochromic film prepared by the invention has the advantages that the transmittance change can reach 85% under the condition of 0.5M H 2 SO 4 solution as electrolyte and 630nm wavelength, the coloring and fading time is 1.8s and 1.8s, the coloring efficiency is 65.9cm 2 /C, and the color is stable in more than 10000 cycles of cyclic test.

Inventors

  • ZHENG JINYOU
  • SUN QIMENG
  • LI SONGJIE
  • YU XIAOMEI

Assignees

  • 郑州大学

Dates

Publication Date
20260508
Application Date
20231103

Claims (6)

  1. 1. The preparation method of the Bi-GO double-doped WO 3 electrochromic film is characterized by comprising the following steps of: Step 1), dissolving tungstic acid in a hydrogen peroxide solution to obtain a peroxytungstic acid solution, adding a bismuth-containing substance into the peroxytungstic acid solution, and dissolving the bismuth-containing substance to obtain a Bi-peroxytungstic acid solution; Step 2), adding graphene-based material nano-sheet dispersion liquid into the Bi-peroxytungstic acid solution obtained in the step 1), stirring and heating to form uniform Bi-GO-peroxytungstic acid sol; step 3), spin-coating the Bi-GO-peroxytungstic acid sol obtained in the step 2) on a conductive glass substrate, and roasting to obtain the conductive glass substrate; The preparation method of the Bi-GO-peroxytungstic acid sol in the step 2) comprises the steps of adding graphene-based material nanosheet dispersion liquid into the Bi-peroxytungstic acid solution, and stirring and heating for 4-12 h at 50-100 ℃ to obtain the Bi-GO-peroxytungstic acid sol; The mass ratio of the graphene-based material to the tungstic acid is 0.0001-0.03:1, and the concentration of the graphene-based material nano-sheet dispersion liquid is 0.5-8 mg/mL; The Bi-peroxytungstic acid solution is prepared by adding bismuth-containing substances into the peroxytungstic acid solution, sealing, and heating at 60-100 ℃ for 4-12 hours, wherein the bismuth-containing substances are one or more of bismuth trioxide, bismuth powder and bismuth nitrate, the number ratio of tungsten atoms to bismuth atoms in the Bi-peroxytungstic acid solution is 1:30, each g of the tungstic acid corresponds to 5-10 mL of hydrogen peroxide solution, and the volume ratio of the Bi-peroxytungstic acid solution to the graphene-based material nanosheet dispersion is 10-2:1; The mass percentage concentration of the hydrogen peroxide solution in the step 1) is 15-50%, and the molar concentration of the peroxytungstic acid solution is 0.1-1M.
  2. 2. The method for preparing the Bi-GO double-doped WO 3 electrochromic film according to claim 1, wherein the graphene-based material in step 2) is graphene oxide or redox graphene.
  3. 3. The method for preparing the Bi-GO double-doped WO 3 electrochromic film according to claim 1, wherein the conductive glass substrate in step 3) is a fluorine-doped tin oxide glass substrate, the baking temperature is 100-600 ℃, and the baking time is 0-6 h.
  4. 4. The Bi-GO double-doped WO 3 electrochromic film is characterized in that the Bi-GO double-doped WO 3 electrochromic film is prepared by the preparation method of the Bi-GO double-doped WO 3 electrochromic film.
  5. 5. The Bi-GO double-doped WO 3 electrochromic film of claim 4, wherein the Bi-GO double-doped WO 3 electrochromic film has an amorphous structure.
  6. 6. A glass, characterized in that the glass contains the Bi-GO double-doped WO 3 electrochromic film as described in claim 4, and the glass is applied to building doors and windows or glass curtain walls.

Description

Bi-GO double-doped WO 3 electrochromic film and preparation method and application thereof Technical Field The invention belongs to the technical field of electrochromic material preparation, and particularly relates to a Bi-GO double-doped WO 3 electrochromic film, a preparation method and application thereof. Background Buildings consume 30-40% of the world's primary energy, most of which is used for cooling, heating, lighting and electrical appliances, with about 30% of the energy lost through windows. Windows are critical to the operation and comfort of a building, while electrochromic glasses can dynamically change color to adjust visible and near infrared radiation according to applied voltages, one of the solutions to reduce energy loss of a building. Compared with the organic electrochromic material, the transition metal oxide material is easy to process, has good reversibility and strong electrochemical stability, and is widely favored. Among them, tungsten trioxide (WO 3) is an electrochromic material with great development prospect, and has the advantages of large light modulation range, high coloring efficiency, low price and the like. In addition, compared with the crystal WO 3, the amorphous WO 3 film has better electrochromic property, faster switching response speed in the visible light and near infrared region and higher color development efficiency. However, the cycle stability is not ideal due to the high disorder of the amorphous WO 3 structure and the weak adhesion to the substrate. The invention patent with the application publication number of CN116789368A discloses a Bi-doped WO 3 electrochromic film, a preparation method and glass, wherein the Bi-doped WO 3 electrochromic film takes 0.5M H 2 SO4 solution as electrolyte, the transmittance change can reach 73% under the condition of 630nm wavelength, the coloring and fading time is 3.6s and 1.4s, the coloring efficiency is 52.52cm 2/C, the stability is maintained after more than 1600 cycles of test, and the coloring efficiency and the cycle stability of the Bi-doped WO 3 electrochromic film are poor. Disclosure of Invention The invention aims to provide a Bi-GO double-doped WO 3 electrochromic film, the coloring efficiency of the Bi-GO double-doped WO 3 electrochromic film is 65.9cm 2/C, and the film is stable in more than 10000 cycles of cyclic tests. The second object of the invention is to provide a preparation method of the Bi-GO double-doped WO 3 electrochromic film. The third object of the invention is to provide an application of the Bi-GO double-doped WO 3 electrochromic film. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The preparation method of the Bi-GO double-doped WO 3 electrochromic film comprises the following steps: Step 1), dissolving tungstic acid in a hydrogen peroxide solution to obtain a peroxytungstic acid solution, adding a bismuth-containing substance into the peroxytungstic acid solution, and dissolving the bismuth-containing substance to obtain a Bi-peroxytungstic acid solution; Step 2), adding graphene-based material nano-sheet dispersion liquid into the Bi-peroxytungstic acid solution obtained in the step 1), stirring and heating to form uniform Bi-GO-peroxytungstic acid sol; And 3) spin-coating the Bi-GO-peroxytungstic acid sol obtained in the step 2) on a conductive glass substrate, and roasting to obtain the conductive glass substrate. Further, the graphene-based material in the step 2) is graphene oxide or graphene oxide-reduction. Further, the preparation method of the Bi-GO-peroxytungstic acid sol in the step 2) comprises the steps of adding graphene-based material nano-sheet dispersion liquid into the Bi-peroxytungstic acid solution, and stirring and heating for 4-12 hours at 50-100 ℃ to obtain the Bi-GO-peroxytungstic acid sol. Further, the mass ratio of the graphene-based material to the tungstic acid is 0.0001-0.03:1, and the concentration of the graphene-based material nano-sheet dispersion liquid is 0.5-8 mg/mL. The Bi-peroxytungstic acid solution is prepared by adding a bismuth-containing substance into the peroxytungstic acid solution, sealing, and heating at 60-100 ℃ for 4-12 hours, wherein the bismuth-containing substance is one or more of bismuth trioxide, bismuth powder and bismuth nitrate, the number ratio of tungsten atoms to bismuth atoms in the Bi-peroxytungstic acid solution is 1:30, each g of the tungstic acid corresponds to 5-10 mL of hydrogen peroxide solution, and the volume ratio of the Bi-peroxytungstic acid solution to the graphene-based material nano-sheet dispersion liquid is 10-2:1. Further, the mass percentage concentration of the hydrogen peroxide solution in the step 1) is 15-50%, and the molar concentration of the peroxytungstic acid solution is 0.1-1M. Further, the conductive glass substrate in the step 3) is a fluorine doped tin oxide glass substrate, the baking temperature is 100-600 ℃, and the baking time is 0-6