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CN-121995677-A - Ion cache type flexible all-solid-state electrochromic device and preparation method thereof

CN121995677ACN 121995677 ACN121995677 ACN 121995677ACN-121995677-A

Abstract

The invention provides an ion cache type flexible all-solid-state electrochromic device and a preparation method thereof, wherein the ion cache type flexible all-solid-state electrochromic device comprises a first flexible base layer, a first conductive layer, a partition ion cache layer, an electrochromic layer, a solid electrolyte layer, a counter electrode layer, a second conductive layer and a second flexible base layer which are sequentially stacked; the partitioned ion cache layer is provided with grid type ion cache units. According to the flexible electrochromic device provided by the invention, the ion buffer layer designed in a partition mode is utilized to provide ion release and storage, lithium ion supply is supplemented for ion transmission blocking caused by the bending process of the device, the electrochromic performance of the all-solid-state electrochromic device under the bending condition is improved, the attenuation rate of the dimming amplitude of the device under the bending condition is effectively reduced, and the dimming uniformity is improved.

Inventors

  • YAO SHUN
  • ZHANG WEIFENG
  • YAO LIJUN
  • WANG YUCONG
  • SHEN DONGDONG

Assignees

  • 浙江景昇薄膜科技有限公司
  • 宁波江丰电子材料股份有限公司

Dates

Publication Date
20260508
Application Date
20260226

Claims (10)

  1. 1. The ion cache type flexible all-solid-state electrochromic device is characterized by comprising a first flexible base layer, a first conductive layer, a partition ion cache layer, an electrochromic layer, a solid electrolyte layer, a counter electrode layer, a second conductive layer and a second flexible base layer which are sequentially stacked, wherein the partition ion cache layer comprises grid type ion cache units.
  2. 2. The ion cache flexible all-solid-state electrochromic device according to claim 1, wherein the material of the grid-type ion cache unit comprises Li 3 PO 4 and/or Li 2 SO 3 ; preferably, the grid type ion cache unit is rectangular and/or hexagonal in shape; preferably, the side length of the grid type ion cache unit is 4-6mm; Preferably, the grid type ion buffer units are formed by isolating separation strips; Preferably, the width of the insulating separation bars is 100-200nm; preferably, the material of the insulating separation strip comprises polyimide; Preferably, the thickness of the partition ion buffer layer is 1-2 μm.
  3. 3. The ion cache flexible all-solid-state electrochromic device according to claim 1 or 2, characterized in that the thickness of the electrochromic layer is 300-500nm; Preferably, the material of the electrochromic layer comprises tungsten trioxide.
  4. 4. The ion cache flexible all-solid-state electrochromic device according to any of claims 1-3, wherein the thickness of the solid-state electrolyte layer is 2-3 μιη; Preferably, the material of the solid electrolyte layer comprises LiPO 4 -P 2 O 5 composite electrolyte; Preferably, in the LiPO 4 -P 2 O 5 composite electrolyte, the content of LiPO 4 is 60-80mol% and the content of P 2 O 5 is 20-40mol%.
  5. 5. The ion cache flexible all-solid-state electrochromic device according to any of claims 1-4, characterized in that the thickness of the ion cache flexible all-solid-state electrochromic device is 50-100 μm.
  6. 6. The ion cache flexible all-solid-state electrochromic device according to any one of claims 1-5, wherein the counter electrode layer has a thickness of 200-400nm; Preferably, the material of the counter electrode layer includes nickel oxide; preferably, the thickness of the first conductive layer is 100-150nm; Preferably, the material of the first conductive layer includes indium tin oxide; preferably, the thickness of the second conductive layer is 100-150nm; preferably, the material of the second conductive layer includes indium tin oxide.
  7. 7. The ion cache flexible all-solid-state electrochromic device according to any of claims 1-6, wherein the material of the first flexible base layer comprises polyethylene terephthalate; preferably, the material of the second flexible substrate comprises polyethylene terephthalate.
  8. 8. A method of manufacturing an ion cache flexible all-solid-state electrochromic device according to any one of claims 1 to 7, comprising the steps of: A first conductive layer is deposited on the first flexible substrate by a magnetron sputtering method, and a second conductive layer, a counter electrode layer, a solid electrolyte layer and an electrochromic layer are sequentially deposited on the second flexible substrate; and preparing a partition ion buffer layer on the electrochromic layer, then laminating the first flexible substrate and the second flexible substrate in a counterpoint manner, and packaging to obtain the ion buffer type flexible all-solid-state electrochromic device.
  9. 9. The preparation method of the partition ion buffer layer according to claim 8, wherein the preparation method comprises the steps of forming an insulation partition strip according to a grid structure coating material, mixing lithium salt, an organic precursor and a solvent to form a precursor solution, filling the precursor solution into a partition formed by the insulation partition strip, and sequentially performing pre-drying and curing heat treatment; preferably, the organic precursor comprises phosphate compounds and/or phosphite compounds; preferably, the phosphate compound comprises triethyl phosphate and/or trimethyl phosphate; preferably, the phosphite ester compound comprises triethyl phosphite and/or trimethyl phosphite; Preferably, the pre-drying temperature is 50-70 ℃; preferably, the temperature of the curing heat treatment is 120-150 ℃.
  10. 10. The method of claim 8 or 9, further comprising plasma treating the surface of the first conductive layer and/or electrochromic layer prior to preparing the partitioned ion cache layer.

Description

Ion cache type flexible all-solid-state electrochromic device and preparation method thereof Technical Field The invention belongs to the technical field of electrochromic, and particularly relates to an ion cache type flexible all-solid-state electrochromic device and a preparation method thereof. Background Electrochromic devices have wide application prospects in the fields of intelligent windows, wearable equipment and the like due to the advantages of reversible adjustment of optical transmittance, low energy consumption and the like. Compared with liquid or gel electrolyte devices, all-solid electrochromic devices are the current research hot spot due to no leakage risk, strong environmental adaptability and high structural stability. With the rapid development of flexible electronics, curved surface display and the like, the requirements of flexible all-solid-state electrochromic devices capable of adapting to bending and folding are increasingly urgent. However, existing flexible all-solid-state electrochromic devices face serious reliability challenges during practical bending applications. Because of the difference of mechanical properties of the materials of the functional layers, the stress generated by repeated bending is easy to cause microcrack or delamination at an interlayer interface, and the continuity of an ion transmission channel is broken, so that the local transmission of lithium ions between an electrochromic layer and an electrolyte layer is blocked. Meanwhile, the uneven distribution of bending stress can cause the excessive consumption of lithium ions in certain areas of the device, and the whole device system can not realize regional accurate supplement, so that the problems of local color change dullness, corresponding speed reduction, complete failure of uneven dimming setting and the like are caused. This bottleneck severely restricts the popularization of such devices in application scenarios requiring frequent bending or small radius of curvature. The prior art is mainly improved in two aspects, namely, a self-repairing interface layer based on supermolecule action such as ureido pyrimidinone is introduced in the material and interface layer, and crack repairing is realized by utilizing reversible hydrogen bonds, however, the method is mainly aimed at repairing physical cracks, the problems of local lithium ion loss and supplementation cannot be fundamentally solved, the repairing times are limited, and the adaptability to smaller bending radius is insufficient. Secondly, the concentration of lithium salt in the solid electrolyte is improved, however, the unbalance of electronic conductivity, the reduction of mechanical strength and the ion agglomeration are easily caused by simply improving the concentration of lithium ions, and the integral response speed and the circulation stability of the device are affected. Therefore, there is a need to provide a flexible all-solid-state electrochromic device design that overcomes the current shortcomings and improves the bending resistance and bending color uniformity. Disclosure of Invention The invention aims to provide an ion cache type flexible all-solid-state electrochromic device and a preparation method thereof, and bending performance of the flexible all-solid-state electrochromic device is improved. In order to achieve the aim of the invention, the invention adopts the following technical scheme: in a first aspect, the invention provides an ion cache type flexible all-solid-state electrochromic device, which comprises a first flexible base layer, a first conductive layer, a partition ion cache layer, an electrochromic layer, a solid electrolyte layer, a counter electrode layer, a second conductive layer and a second flexible base layer which are sequentially stacked, wherein the partition ion cache layer comprises grid type ion cache units. The electrochromic device provided by the invention adopts a layered symmetrical structure, a partitioned ion cache layer which adopts a partition form to design an ion cache unit is arranged between the first conductive layer and the electrochromic layer which are positioned on the outer layer, and the ion cache unit contains a solid electrolyte material and has good lithium ion storage capacity and chemical stability, so that an ion storage function is provided. When the device is bent by external force, microcracks are generated between layers of a bending area, so that ion transmission in a solid electrolyte layer is blocked, the ion supply of the electrochromic layer in the area is insufficient, at the moment, the ion buffer units in the corresponding area can rapidly release and supplement stored Li + to the electrochromic layer, the ion release/intercalation reaction is ensured to be carried out, the device is ensured to be uniformly discolored, and when the bending stress of the device disappears, the ion buffer units can reversely supplement ions in the solid electrolyte layer t