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CN-117406510-B - Double-ion cooperative work long-life electrochromic device and preparation method thereof

CN117406510BCN 117406510 BCN117406510 BCN 117406510BCN-117406510-B

Abstract

The invention relates to a long-life electrochromic device with double-ion cooperative work and a preparation method thereof. The long-life electrochromic device with the double-ion cooperative work comprises a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer and a second transparent electrode layer which are sequentially stacked, wherein the electrolyte layer is made of aluminum salt, preferably at least one of aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate and aluminum chloride, and the gel-based ion storage layer is a gel-based solid electrolyte containing lithium salt.

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 (10)

  1. 1. The double-ion cooperative work long-life electrochromic device is characterized by comprising a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer and a second transparent electrode layer which are sequentially stacked; the electrolyte layer is made of aluminum salt; The gel-based ion storage layer is a gel-based solid electrolyte containing lithium salt, the gel-based ion storage layer also contains magnesium salt, the magnesium salt is at least one of magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium silicate, magnesium nitrate and magnesium sulfate, and the molar ratio of the lithium salt to the magnesium salt is 1 (0.05-0.2).
  2. 2. The dual ion cooperating long life electrochromic device according to claim 1, wherein the material of the electrolyte layer is at least one of aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate, aluminum chloride.
  3. 3. The dual-ion cooperative work long-life electrochromic device according to claim 1, wherein the inorganic electrochromic layer is made of at least one of WO 3 、MoO 3 and TiO 2 , and the thickness of the inorganic electrochromic layer is 100-500 nm.
  4. 4. The dual ion cooperative long life electrochromic device of claim 1, wherein the electrolyte layer has a thickness of 50-300 nm.
  5. 5. The double-ion cooperative work long-life electrochromic device according to claim 1, wherein the thickness of the gel-based ion storage layer is 20-80 μm, and the lithium salt is at least one of lithium chloride, lithium perchlorate, lithium phosphate and lithium silicate.
  6. 6. The dual-ion cooperative working life electrochromic device according to claim 1, wherein the materials of the first transparent electrode layer and the second transparent electrode layer are independently selected from at least one of transparent conductive oxide and metal nanowire, the sheet resistance of the first transparent electrode layer and the second transparent electrode layer is 10-40 Ω/cm 2 , and the transmittance is not less than 75%.
  7. 7. A method of making a dual ion co-operating long life electrochromic device according to claim 1, wherein said method of making a gel-based ion storage layer comprises: (1) Weighing the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium salt according to the molar ratio of 1 (1-3) (0.05-0.2) (0.5-2) (1-3), and stirring in a dark place until the photo-curing resin, the solvent, the stabilizer, the organic precursor and the lithium salt are completely dissolved to obtain a mixed solution 1; (2) Adding magnesium salt and an initiator into the mixed solution 1 to obtain a mixed solution 2, wherein the anions of the magnesium salt are the same as those of the lithium salt; (3) And (3) spin-coating the obtained mixed solution 2, and photo-curing under an ultraviolet lamp to obtain the gel-based ion storage layer.
  8. 8. The method according to claim 7, wherein the photocurable resin is at least one selected from the group consisting of tetter TTA21, L-6206, L-6380H, L-6605; The solvent is at least one of PMA, NMP, MDBE and EMC; The stabilizer is a transition metal organic compound; the organic precursor comprises an acid ester compound; The rotating speed of the spin coating is 1000-3000 rpm, and the time is 10-60 s; the light curing is carried out by irradiating an ultraviolet lamp with the power of 100-300W for 5-30 seconds.
  9. 9. The method according to claim 7, wherein the mixed solution 2 further comprises at least one of a leveling agent, an adhesion promoter, and an antifoaming agent; The leveling agent is at least one of BYK333, BYK358N, BYK, BYK378, and the addition amount is 0.5-2% of the total mass of the precursor; the adhesion promoter is at least one of BYK4500, BYK4509, BYK4510 and BYK4511, and the addition amount is 0.05-0.2% of the total mass of the precursor; The defoamer is at least one of BYK011, BYK012 and BYK014, and the addition amount of the defoamer is 0.1-0.5% of the total mass of the precursor.
  10. 10. The method of claim 7, wherein the electrochromic layer is formed on the surface of the first transparent electrode layer by magnetron sputtering, laser pulse deposition, molecular beam epitaxy, spin coating, spray coating, or a czochralski method.

Description

Double-ion cooperative work long-life electrochromic device and preparation method thereof Technical Field The invention relates to a long-life electrochromic device with double-ion cooperative work and a preparation method thereof, 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. 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, the response speed of the all-solid-state electrochromic device is low due to the low ion migration speed, so that the application field of the all-solid-state electrochromic device is limited. On the other hand, all-solid-state electrochromic devices are prone to uneven coloration after multiple cycles, making it difficult to design and manufacture large-sized devices. Dual ion operated devices offer significant advantages over single ion devices, including better tuning capabilities, response speed, and better cycling stability due to lower drive voltages. It is therefore expected that the above problems can be solved to design a device for co-migration of double ions and even multiple ions. Typically, the conductive ions of a dual ion controlled electrochromic device are provided by a single compound, however, the difference in chemical potential of the different ions during cycling will result in a change in the proportion of ions during migration. Such disadvantageous variations will shorten the cycling stability of the device. Disclosure of Invention Aiming at the technical problem that the cycling stability of the device is reduced due to the fact that recombination caused by ion migration speed is easy to occur in the cycling process of the conventional double-ion working electrochromic device, the invention provides a double-ion cooperative working long-service-life electrochromic device and a preparation method thereof. On one hand, the invention provides a double-ion cooperative long-life electrochromic device and a preparation method thereof, wherein the double-ion cooperative long-life electrochromic device comprises a first transparent electrode layer, an inorganic electrochromic layer, an electrolyte layer, a gel-based ion storage layer and a second transparent electrode layer which are sequentially stacked, the electrolyte layer is made of at least one of aluminum salt, preferably aluminum silicate, aluminum phosphate, aluminum borate, aluminum perchlorate and aluminum chloride, and the gel-based ion storage layer is a gel-based solid electrolyte containing lithium salt. In the patent, a dielectric layer and an ion storage layer respectively containing migration ions are connected in series, and double-ion cooperative migration is realized by utilizing a cation 'unlocking effect'. The ion migration mode can realize the fixation of the migration proportion of two ions, so that the cycle stability of the device is obviously improved. Therefore, the Al and Li with the series structure are designed to be used as co-migration ions, and compared with the traditional aluminum lithium silicate and oth