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CN-117406514-B - Electrochromic device with high-low temperature tolerance

CN117406514BCN 117406514 BCN117406514 BCN 117406514BCN-117406514-B

Abstract

The invention relates to an electrochromic device with strong high-low temperature tolerance. The electrochromic device with high and low temperature tolerance comprises a first transparent electrode, an electrochromic layer, a composite gel electrolyte layer and a second transparent electrode which are sequentially stacked, wherein the composite gel electrolyte layer is obtained by coating and curing a mixed solution obtained by mixing an alginate solution and resin slurry containing cations.

Inventors

  • CAO XUN
  • HUANG AIBIN
  • XU FANG
  • JI XIAOWEI

Assignees

  • 中国科学院上海硅酸盐研究所

Dates

Publication Date
20260512
Application Date
20220707

Claims (13)

  1. 1. The electrochromic device with high and low temperature tolerance is characterized by comprising a first transparent electrode, an electrochromic layer, a composite gel electrolyte layer and a second transparent electrode which are sequentially stacked, wherein the composite gel electrolyte layer is obtained by coating and curing a mixed solution obtained by mixing an alginate solution and resin slurry containing cations.
  2. 2. The electrochromic device according to claim 1, wherein the mass concentration of the alginate solution is 0.5-5 wt%, the solvent of the alginate solution is at least one of PMA, NMP and EMC, and the alginate is at least one of sodium alginate, aluminum alginate, magnesium alginate and calcium alginate.
  3. 3. The electrochromic device according to claim 2, wherein the alginate solution further comprises a complexing agent, and the complexing agent is at least one selected from 8-hydroxyquinoline, ethylenediamine, EDTA beta-gluconolactone, glucono-a-lactone and glucono delta lactone, and the concentration is 1-5wt%.
  4. 4. The electrochromic device according to claim 1, wherein the resin paste containing cations comprises a solvent, a stabilizer, a curing resin, an organic precursor and an ion source, and the mass ratio of the solvent, the stabilizer, the curing resin, the organic precursor and the ion source is (0.5-2): 0.1-3): 1-10): 0.05-5): 1.
  5. 5. The electrochromic device according to claim 4, wherein the ratio of solvent, stabilizer, cured resin, organic precursor and ion source is 1:1:2:0.1:1.
  6. 6. The electrochromic device according to claim 4, wherein the solvent is selected from at least one of PMA, NMP and EMC; the stabilizer is selected from at least one of ferrocene, vinyl ferrocene; The curing resin is at least one selected from ultraviolet curing resin, PVB resin, organic silicon resin and acrylic resin; the organic precursor is at least one of ETPTA, TMPTA and trimethylolpropane triacrylate; the ion source is selected from at least one of an Al ion salt, an Mg ion salt and a Ca ion salt.
  7. 7. The electrochromic device according to claim 6, wherein the ion source is at least one of magnesium perchlorate, calcium perchlorate, and aluminum perchlorate.
  8. 8. The electrochromic device according to claim 1, characterized in that the mass ratio of the alginate solution and the resin paste containing cations is (1% -50%): 1.
  9. 9. The electrochromic device according to claim 1, wherein an adhesion promoter and a leveling agent are also added to the mixed solution; The adhesion promoter is at least one of BYK4500, BYK4509, BYK4510, BYK4511 and BYK4512, and the addition amount is 0.1-5wt%; the leveling agent is BYK333, BYK358N, BYK, BYK378, and the addition amount is 0.5-2wt%.
  10. 10. The electrochromic device according to claim 1, characterized in that the coating is spin-coating at a rotational speed of 1000-3000 rpm; The curing mode is ultraviolet light curing or heat curing, wherein the power of the ultraviolet light curing is 50-200W, the time is 5-60 s, the temperature of the heat curing is 50-80 ℃ and the time is 30-120 minutes; The thickness of the composite gel electrolyte layer is 20-80 mu m.
  11. 11. The electrochromic device according to claim 1, wherein the electrochromic layer is an inorganic electrochromic layer, the material is at least one selected from WO 3 、MoO 3 and TiO 2 , and the thickness of the electrochromic layer is 100-500 nm.
  12. 12. The electrochromic device according to claim 1, wherein the first transparent electrode and the second transparent electrode are made of at least one material selected from transparent conductive oxides and metal nanowires, the sheet resistance of the first transparent electrode and the second transparent electrode is 10-40 Ω/cm 2 , and the average value of the transmittance of visible light wave bands is more than or equal to 75%.
  13. 13. The electrochromic device according to claim 1, characterized in that the electrochromic device is cycled 5000 times at-80 ℃ to 150 ℃ with a tuning capacity decay of 10% or less.

Description

Electrochromic device with high-low temperature tolerance Technical Field The invention relates to an electrochromic device with high and low temperature tolerance, belonging to the technical field of chemical material synthesis and functional materials. Background The energy is an important foundation for maintaining national economic sustainable development and guaranteeing the living standard of people's substances. Today, the problems of energy shortage, environmental pollution and the like are increasingly severe, and scientists are striving to find a method for saving energy and reducing consumption while developing new energy. The electrochromic device and the technology are mainly applied to the fields of energy-saving building glass, other movable body windows, anti-dazzle rearview mirrors of automobiles, display screens, electronic paper, camouflage and the like. Low-E is a Low emissivity glass, and the working principle is that most of infrared rays are reflected, so that heat entering a room is reduced. Hollow glass is a glass that reduces heat exchange between the inside and outside of a room. The aim is to reduce the indoor refrigeration energy consumption. Both windows and their combinations are only advantageous for cooling and cannot be controlled. That is, in winter cold, heat is still difficult to enter the room. Conventional electrochromic devices are composed of five layers of thin films, including two transparent conductive layers, an ion storage layer, an electrochromic layer, and an ion conducting layer. Wherein, the ion storage layer assists the electrochromic layer to apply low voltage on the first and second conductive layers to realize electrochromic reaction. Ion conductive layers are provided with lithium ions and a diffusion film layer, which is responsible for ensuring ion conductivity under the action of an electric field, and the structure and the preparation process of the ion conductive layers are one of the most important technologies for ensuring electrochromic performance of devices. Electrochromic devices can be classified into three types according to the state of an ion conductive layer, namely, liquid electrochromic devices, gel electrochromic devices and all-solid electrochromic devices. The liquid electrochromic device has the advantages of small resistance in the ion migration process, high ion conductivity, high electrochromic speed, high transparency, simple preparation mode and easy filling, but has the problems of liquid leakage, corrosion, uneven distribution and the like, and requires extremely high and extremely fine filling and sealing technology. Along with the repeated circulation of electrochromic reaction, the ion concentration of the electrolyte tends to be unstable, so that the performance of the electrochromic device is seriously weakened, and H + ions in the acidic electrolyte corrode the electrochromic film material, so that the long-term use is not facilitated. In addition, the use safety of organic electrolyte is poor, such as LiClO 4 is easy to explode, is not suitable for long-term storage and transportation, and the organic solvent is not high-temperature resistant, has poor chemical stability, and has the problems of uneven coloring of devices and the like. Gel state electrochromic device adopts gel state ion conducting layer formed by adding some conductive polymer into liquid ion conducting layer, gel state (quasi solid state) ion conducting layer is between solid state and liquid state, its ion conductivity is higher than liquid state electrolyte, it has excellent flexibility and adhesiveness, it can reduce the injury caused by hard substance such as glass when the device is destroyed by external force, but its mechanical strength and uniformity are poor, it can not meet the condition of large-scale industrial production. The all-solid-state electrochromic device has stable structure and good resistance to oxygen and ultraviolet irradiation, and can avoid the defects of the liquid-state device and the quasi-solid-state device. However, since the expansion coefficients of the electrolyte layer are different from those of other film layers, when the gel-state electrolyte layer based on resin is operated in a high-temperature or low-temperature environment, thermal expansion and contraction will cause microcracks or other defects to be generated at the film layers and interfaces thereof. These defects will trap the migrating cations and form dead spots that fail to fade normally, resulting in device failure. Thus, electrochromic devices are subject to significant limitations in high-latitude or low-latitude areas. Disclosure of Invention Aiming at the technical problem that the electrochromic performance of the conventional electrochromic device is rapidly reduced in the extreme environment of high/low temperature to limit the application range and the field, the invention provides the electrochromic device with strong high/low temperature