Electrochromic device with simple structure

Abstract

The invention discloses an electrochromic device with a simple structure, and belongs to the technical field of preparation of electrochromic devices. The electrochromic device with the simple structure is composed of a transparent conducting layer, a color changing layer and an electrolyte, the transparent conducting layer is prepared from 3-(3-bromomethoxy) 4-methylthiophene, 3-(2-octyldodecyl)-thiophene and pyridine-3-boric acid, and the color changing layer is prepared from a transparent conducting layer material and a color changing layer material. The material of the color changing layer is prepared from 5-nitroindole, 2-chloropyrimidine, 3-nitrophenylboronic acid, hydrazine hydrate, m-phenylenediamine and isophthaloyl dichloride, and the material of the electrolyte layer is prepared from acrylamide, lithium chloride and tetramethylethylenediamine. The electrochromic device prepared by the method has excellent thermal stability, excellent color changing performance and good electrochemical performance.

Description

Technical Field

[0001] This invention belongs to the field of electrochromic device fabrication technology, specifically relating to an electrochromic device with a simple structure. Background Technology

[0002] Electrochromism refers to the stable and reversible changes in the optical properties (such as reflectivity, transmittance, and absorptivity) of a material under the influence of an electric field, resulting in reversible changes in color and transparency. This technology brings revolutionary innovation possibilities to fields such as smart windows, displays, optical filters, and smart wearable devices.

[0003] In the research context of electrochromic devices, traditional windows and sunshades often have many limitations. For example, while traditional curtains or blinds can effectively block sunlight, they lack flexibility and cannot automatically adjust according to external light conditions. Electrochromic devices, on the other hand, can precisely control light transmittance by applying or removing an electric field according to ambient light intensity or user needs, achieving intelligent management of indoor light, thereby achieving energy saving, consumption reduction, and improved living comfort.

[0004] Furthermore, with technological advancements and rising demands for quality of life, the application of electrochromic technology in smart devices is increasingly in demand. For example, in augmented reality glasses, electrochromic lenses can automatically adjust their light transmittance according to ambient light, providing users with a more realistic and comfortable visual experience. Simultaneously, electrochromic technology can also be applied to electronic displays, achieving high-definition image display by controlling pixel color changes. Summary of the Invention

[0005] The purpose of this invention is to provide a simple electrochromic device to solve the technical problems of complex structure, poor color-changing effect and thermal stability of existing electrochromic devices.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: This invention provides a simple electrochromic device comprising a transparent conductive layer, a color-changing layer, and an electrolyte. The transparent conductive layer is prepared from 3-(3-bromomethoxy)4-methylthiophene, 3-(2-octyldodecyl)thiophene, and pyridine-3-boronic acid. The color-changing layer is prepared from 5-nitroindole, 2-chloropyrimidine, 3-nitrophenylboronic acid, hydrazine hydrate, m-phenylenediamine, and isophthaloyl chloride. The electrolyte layer is prepared from acrylamide, lithium chloride, and tetramethylethylenediamine.

[0007] Preferably, the method for preparing the transparent conductive layer material includes the following steps: Q1: 3-(3-bromomethoxy)4-methylthiophene was added to tetrahydrofuran and stirred to dissolve. After that, trimethylamine aqueous solution was added and stirred at room temperature. The mixture was then dried by rotary evaporation. Tetrahydrofuran was added and stirred. The mixture was filtered, washed, and dried to obtain compound 1. Q2: 3-(3-bromomethoxy)4-methylthiophene, compound 1 and 3-(2-octyldodecyl)thiophene were added to chloroform, followed by the addition of ferric chloride. The mixture was heated and stirred under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, added to methanol, followed by the addition of hydrazine hydrate. The mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Pyridine-3-boronic acid was added to a mixed solution of N,N-dimethylformamide and tetrahydrofuran containing compound 2. Under nitrogen protection, the mixture was heated and stirred, cooled, concentrated, and then added dropwise to tetrahydrofuran for precipitation. The mixture was filtered, washed, dissolved in distilled water, dialyzed, and freeze-dried to obtain a transparent conductive layer material.

[0008] The synthesis reaction formula for the transparent conductive layer material in the above process is as follows: Preferably, in Q1, the ratio of 3-(3-bromomethoxy)4-methylthiophene to trimethylamine aqueous solution is (2.12-2.77) g: (42-58) mL, the mass fraction of trimethylamine aqueous solution is 30 wt%, the stirring reaction time is 40-50 h, tetrahydrofuran is added and stirred for 30-45 min, and then washed with tetrahydrofuran.

[0009] Preferably, in Q2, the ratio of 3-(3-bromomethoxy)4-methylthiophene, compound 1, 3-(2-octyldodecyl)thiophene, chloroform, ferric chloride, and hydrazine hydrate is (0.21-0.27) g : (0.24-0.38) g : (0.13-0.25) g : (28-35) mL : (0.93-1.08) g : (0.05-0.08) g, the heating and stirring reaction temperature is 30-40℃, and the reaction time is 42-54 h.

[0010] Preferably, in Q3, the ratio of pyridine-3-boronic acid, compound 2, N,N-dimethylformamide, tetrahydrofuran, and the amount of tetrahydrofuran added is (0.29-0.38) g : (0.21-0.28) g : (10-20) mL : (10-20) mL : (90-110) mL. The heating and stirring temperature is 90-95℃, the stirring time is 42-54 h, and the mixture is washed with tetrahydrofuran. During dialysis, the molecular cutoff of the dialysis bag is 3500 kDa, and the dialysis time is 2-4 days.

[0011] Preferably, the method for preparing the color-changing layer material includes the following steps: S1: Under nitrogen protection, 5-nitroindole and N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. Sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred. Under ice bath conditions, N,N-dimethylformamide containing 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred. The mixture was then reacted in an oil bath. After the reaction was complete, the container was cooled, distilled water was added, and the mixture was filtered, washed, and dried to obtain intermediate A. S2: Add intermediate A, 3-nitrophenylboronic acid, silver trifluoroacetate, dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and trifluoroethanol to a container and react in an oil bath. After the reaction is complete, cool, add triethylamine and stir, filter, wash and purify to obtain intermediate B. S3: Under nitrogen protection, intermediate B, palladium / carbon, and ethanol were added to a container and refluxed in an oil bath. Then, hydrated hydrazine was added, and the reflux reaction continued. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, m-phenylenediamine, intermediate C, and N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred to react. Subsequently, calcium hydroxide was added, and the mixture was stirred, washed, and dried to obtain the color-changing layer material.

[0012] The synthesis reaction formula for the color-changing layer material in the above process is as follows: The mass spectrometry analysis results of intermediate A were: m / z: 240.06 (100.0%), 241.07 (13.1%), 241.06 (1.5%), 242.07 (1.4%); the mass spectrometry analysis results of intermediate B were: m / z: 361.08 (100.0%), 362.08 (21.3%), 363.09 (2.7%); and the mass spectrometry analysis results of intermediate C were: m / z: 301.13 (100.0%), 302.14 (19.6%), 302.13 (1.8%), 303.14 (1.8%).

[0013] Preferably, in S1, the ratio of 5-nitroindole, sodium hydride, and 2-chloropyrimidine is (3.12-3.38) g : (1.01-1.12) g : (2.43-2.97) g, the stirring time at room temperature is 30-45 min, the stirring time under heating is 30-45 min, the oil bath reaction temperature is 120-140℃, the reaction time is 6-8 h, the product is first washed with N,N-dimethylformamide, then washed with distilled water, the drying temperature is 60-70℃, and the drying time is 20-24 h.

[0014] Preferably, in S2, the ratio of intermediate A, 3-nitrophenylboronic acid, silver trifluoroacetate, dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and trifluoroethanol is (0.034-0.055) g : (0.042-0.055) g : (0.172-0.186) g : (0.0015-0.0018) : (2-3) mL, the oil bath reaction temperature is 80-90℃, the reaction time is 6-9 h, and the stirring time is 5-10 min.

[0015] Preferably, in step S3, the ratio of intermediate B, palladium / carbon, ethanol, and hydrated hydrazine is (1.63-2.01) g : (0.21-0.28) g : (45-55) mL : (10-15) mL, the oil bath reflux reaction temperature is 80-90℃, the reaction time is 3-5 h, and the reflux reaction time is continued for 30-45 min; the ratio of m-phenylenediamine, intermediate C, N,N-dimethylacetamide, isophthaloyl chloride, and calcium hydroxide is (1.05-1.13) g : (2.63-3.04) g : (80-102) mL : (1.62-1.93) g : (6.8-7.6) g, the heating and stirring reaction temperature is 60-70℃, the reaction time is 1-2 h, and the stirring time is continued for 10-20 min.

[0016] Preferably, a method for fabricating a simple electrochromic device includes the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0017] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: This invention first prepares a transparent conductive layer material using 3-(3-bromomethoxy)4-methylthiophene, 3-(2-octyldodecyl)thiophene, and pyridine-3-boronic acid. Then, a color-changing layer material is prepared using 5-nitroindole, 2-chloropyrimidine, 3-nitrophenylboronic acid, hydrazine hydrate, m-phenylenediamine, and isophthaloyl chloride as raw materials. Applying this material to the fabrication of electrochromic devices effectively improves their conductivity, electrochromic performance, and excellent thermal stability. Furthermore, the electrochromic devices prepared by this method have a simple structure and a straightforward manufacturing process. The high π-electron cloud density in the thiophene structure of the transparent conductive layer material promotes the formation of delocalized electrons, endowing the transparent conductive layer material with conductivity, which is achieved through electron transfer between molecular chains. Simultaneously, under the influence of voltage or current, thiophene polymers can undergo reversible redox reactions, leading to changes in the electronic structure of the molecular chains, thereby producing rich color changes and meeting the requirements of electrochromic devices for transparent conductive layer materials. The indole groups in the prepared chromatic layer material possess unique electronic structures and absorption spectral characteristics, enabling it to exhibit diverse color changes under voltage or current stimulation. Furthermore, the polyamide structure in the chromatic layer material exhibits high amide bond energy, excellent chemical and thermal stability, resulting in electrochromic devices with long service life and high heat resistance. Detailed Implementation

[0018] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1: This example discloses a method for preparing a transparent conductive layer material, including the following steps: Q1: 2.45 g of 3-(3-bromomethoxy)4-methylthiophene was added to 20 mL of tetrahydrofuran and stirred until dissolved. Then, 50 mL of 30 wt% trimethylamine aqueous solution was added. The mixture was stirred at room temperature for 48 h and then dried by rotary evaporation. Tetrahydrofuran was added and stirred for 45 min. The mixture was filtered, washed with tetrahydrofuran, and dried to obtain compound 1. Q2: 0.24 g of 3-(3-bromomethoxy)4-methylthiophene, 0.31 g of compound 1 and 0.19 g of 3-(2-octyldodecyl)thiophene were added to 31 mL of chloroform, followed by the addition of 1.01 g of ferric chloride. The mixture was heated and stirred at 40 °C for 48 h under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, and added to methanol. Then, 0.065 g of hydrazine hydrate was added, and the mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Add 0.33g of pyridine-3-boronic acid to a mixed solution of 15mL N,N-dimethylformamide and 15mL tetrahydrofuran containing 0.24g of compound 2. Under nitrogen protection, heat and stir at 90℃ for 48h, cool, concentrate, and add dropwise to 100mL tetrahydrofuran for precipitation. Filter, wash with tetrahydrofuran, dissolve in distilled water, dialyze, the molecular cutoff of the dialysis bag is 3500kDa, the dialysis time is 3 days, freeze-dry to obtain a transparent conductive layer material.

[0020] This embodiment discloses a method for preparing a color-changing layer material, including the following steps: S1: Under nitrogen protection, 3.25 g of 5-nitroindole and 40 mL of N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. 1.06 g of sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred for 45 min. Under ice bath conditions, 10 mL of N,N-dimethylformamide containing 2.65 g of 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred for 30 min. The mixture was then reacted in an oil bath at 130 °C for 8 h. After the reaction was completed, the container was cooled, distilled water was added, and the mixture was filtered. The mixture was first washed with N,N-dimethylformamide and then with distilled water. The mixture was dried at 70 °C for 24 h to obtain intermediate A. S2: 0.045g of intermediate A, 0.048g of 3-nitrophenylboronic acid, 0.178g of silver trifluoroacetate, 0.0016g of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and 2.5mL of trifluoroethanol were added to a container and reacted in an oil bath at 90℃ for 8h. After the reaction was completed, the mixture was cooled, 3 drops of triethylamine were added and stirred for 10min. The mixture was then filtered, washed, and purified to obtain intermediate B. S3: Under nitrogen protection, 1.82 g of intermediate B, 0.24 g of palladium / carbon, and 50 mL of ethanol were added to a container and refluxed in an oil bath at 90 °C for 4 h. Then, 12.5 mL of hydrated hydrazine was added, and the reflux reaction was continued for 45 min. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, 1.09 g of m-phenylenediamine, 2.83 g of intermediate C, and 96 mL of N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, 1.81 g of isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred at 70 °C for 2 h. Then, 7.4 g of calcium hydroxide was added, and the mixture was stirred for 15 min. The mixture was washed and dried to obtain the color-changing layer material.

[0021] This embodiment discloses a method for fabricating a simple electrochromic device, including the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0022] Example 2: This example discloses a method for preparing a transparent conductive layer material, including the following steps: Q1: 2.12 g of 3-(3-bromomethoxy)4-methylthiophene was added to 20 mL of tetrahydrofuran and stirred until dissolved. Then, 42 mL of 30 wt% trimethylamine aqueous solution was added. The mixture was stirred at room temperature for 48 h and then dried by rotary evaporation. Tetrahydrofuran was added and stirred for 45 min. The mixture was filtered, washed with tetrahydrofuran, and dried to obtain compound 1. Q2: 0.21 g of 3-(3-bromomethoxy)4-methylthiophene, 0.24 g of compound 1 and 0.13 g of 3-(2-octyldodecyl)thiophene were added to 28 mL of chloroform, followed by 0.93 g of ferric chloride. The mixture was heated and stirred at 40 °C for 48 h under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, added to methanol, followed by 0.05 g of hydrazine hydrate. The mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Add 0.29 g of pyridine-3-boronic acid to a mixed solution of 10 mL of N,N-dimethylformamide and 10 mL of tetrahydrofuran containing 0.21 g of compound 2. Under nitrogen protection, heat and stir at 90 °C for 48 h, cool, concentrate, and add dropwise to 90 mL of tetrahydrofuran for precipitation. Filter, wash with tetrahydrofuran, dissolve in distilled water, dialyze, the molecular cutoff of the dialysis bag is 3500 kDa, the dialysis time is 3 days, freeze-dry to obtain a transparent conductive layer material.

[0023] This embodiment discloses a method for preparing a color-changing layer material, including the following steps: S1: Under nitrogen protection, 3.12 g of 5-nitroindole and 40 mL of N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. 1.01 g of sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred for 45 min. Under ice bath conditions, 10 mL of N,N-dimethylformamide containing 2.43 g of 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred for 30 min. The mixture was then reacted in an oil bath at 130 °C for 8 h. After the reaction was completed, the container was cooled, distilled water was added, and the mixture was filtered. The mixture was first washed with N,N-dimethylformamide and then with distilled water. The mixture was dried at 70 °C for 24 h to obtain intermediate A. S2: 0.034 g of intermediate A, 0.042 g of 3-nitrophenylboronic acid, 0.172 g of silver trifluoroacetate, 0.0015 g of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and 2 mL of trifluoroethanol were added to a container and reacted in an oil bath at 90 °C for 8 h. After the reaction was completed, the mixture was cooled, 3 drops of triethylamine were added and stirred for 10 min, filtered, washed and purified to obtain intermediate B. S3: Under nitrogen protection, 1.63 g of intermediate B, 0.21 g of palladium / carbon, and 45 mL of ethanol were added to a container and refluxed in an oil bath at 90 °C for 4 h. Then, 10 mL of hydrated hydrazine was added, and the reflux reaction was continued for 45 min. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, 1.05 g of m-phenylenediamine, 2.63 g of intermediate C, and 80 mL of N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, 1.62 g of isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred at 70 °C for 2 h. Then, 6.8 g of calcium hydroxide was added, and the mixture was stirred for 15 min. The mixture was washed and dried to obtain the color-changing layer material.

[0024] This embodiment discloses a method for fabricating a simple electrochromic device, including the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0025] Example 3: This example discloses a method for preparing a transparent conductive layer material, including the following steps: Q1: 2.77 g of 3-(3-bromomethoxy)4-methylthiophene was added to 20 mL of tetrahydrofuran and stirred until dissolved. Then, 58 mL of 30 wt% trimethylamine aqueous solution was added. The mixture was stirred at room temperature for 48 h and then dried by rotary evaporation. Tetrahydrofuran was added and stirred for 45 min. The mixture was filtered, washed with tetrahydrofuran, and dried to obtain compound 1. Q2: 0.27 g of 3-(3-bromomethoxy)4-methylthiophene, 0.38 g of compound 1 and 0.25 g of 3-(2-octyldodecyl)thiophene were added to 35 mL of chloroform, followed by 1.08 g of ferric chloride. The mixture was heated and stirred at 40 °C for 48 h under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, added to methanol, followed by 0.08 g of hydrazine hydrate. The mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Add 0.38g of pyridine-3-boronic acid to a mixed solution of 20mL N,N-dimethylformamide and 20mL tetrahydrofuran containing 0.28g of compound 2. Under nitrogen protection, heat and stir at 90℃ for 48h, cool, concentrate, and add dropwise to 110mL tetrahydrofuran for precipitation. Filter, wash with tetrahydrofuran, dissolve in distilled water, dialyze, the molecular cutoff of the dialysis bag is 3500kDa, the dialysis time is 3 days, freeze-dry to obtain a transparent conductive layer material.

[0026] This embodiment discloses a method for preparing a color-changing layer material, including the following steps: S1: Under nitrogen protection, 3.38 g of 5-nitroindole and 40 mL of N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. 1.12 g of sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred for 45 min. Under ice bath conditions, 10 mL of N,N-dimethylformamide containing 2.97 g of 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred for 30 min. The mixture was then reacted in an oil bath at 130 °C for 8 h. After the reaction was completed, the container was cooled, distilled water was added, and the mixture was filtered. The mixture was first washed with N,N-dimethylformamide and then with distilled water. The mixture was dried at 70 °C for 24 h to obtain intermediate A. S2: Add 0.055g of intermediate A, 0.055g of 3-nitrophenylboronic acid, 0.186g of silver trifluoroacetate, 0.0018g of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and 3mL of trifluoroethanol to a container, react in an oil bath at 90℃ for 8h, after the reaction is completed, cool, add 3 drops of triethylamine and stir for 10min, filter, wash and purify to obtain intermediate B; S3: Under nitrogen protection, 2.01 g of intermediate B, 0.28 g of palladium / carbon, and 55 mL of ethanol were added to a container and refluxed in an oil bath at 90 °C for 4 h. Then, 15 mL of hydrated hydrazine was added, and the reflux reaction was continued for 45 min. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, 1.13 g of m-phenylenediamine, 3.04 g of intermediate C, and 102 mL of N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, 1.93 g of isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred at 70 °C for 2 h. Then, 7.6 g of calcium hydroxide was added, and the mixture was stirred for 15 min. The mixture was washed and dried to obtain the color-changing layer material.

[0027] This embodiment discloses a method for fabricating a simple electrochromic device, including the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0028] Example 4: This example discloses a method for preparing a transparent conductive layer material, including the following steps: Q1: 2.28 g of 3-(3-bromomethoxy)4-methylthiophene was added to 20 mL of tetrahydrofuran and stirred until dissolved. Then, 46 mL of 30 wt% trimethylamine aqueous solution was added. The mixture was stirred at room temperature for 48 h and then dried by rotary evaporation. Tetrahydrofuran was added and stirred for 45 min. The mixture was filtered, washed with tetrahydrofuran, and dried to obtain compound 1. Q2: 0.22 g of 3-(3-bromomethoxy)4-methylthiophene, 0.26 g of compound 1 and 0.15 g of 3-(2-octyldodecyl)thiophene were added to 29 mL of chloroform, followed by 0.97 g of ferric chloride. The mixture was heated and stirred at 40 °C for 48 h under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, added to methanol, followed by 0.06 g of hydrazine hydrate. The mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Add 0.31g of pyridine-3-boronic acid to a mixed solution of 12mL N,N-dimethylformamide and 12mL tetrahydrofuran containing 0.23g of compound 2. Under nitrogen protection, heat and stir at 90℃ for 48h, cool, concentrate, and add dropwise to 95mL tetrahydrofuran for precipitation. Filter, wash with tetrahydrofuran, dissolve in distilled water, dialyze, the molecular cutoff of the dialysis bag is 3500kDa, the dialysis time is 3 days, freeze-dry to obtain a transparent conductive layer material.

[0029] This embodiment discloses a method for preparing a color-changing layer material, including the following steps: S1: Under nitrogen protection, 3.17 g of 5-nitroindole and 40 mL of N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. 1.04 g of sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred for 45 min. Under ice bath conditions, 10 mL of N,N-dimethylformamide containing 2.51 g of 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred for 30 min. The mixture was then reacted in an oil bath at 130 °C for 8 h. After the reaction was completed, the container was cooled, distilled water was added, and the mixture was filtered. The mixture was first washed with N,N-dimethylformamide and then with distilled water. The mixture was dried at 70 °C for 24 h to obtain intermediate A. S2: 0.041g of intermediate A, 0.046g of 3-nitrophenylboronic acid, 0.174g of silver trifluoroacetate, 0.0017g of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and 2.1mL of trifluoroethanol were added to a container and reacted in an oil bath at 90℃ for 8h. After the reaction was completed, the mixture was cooled, 3 drops of triethylamine were added and stirred for 10min, filtered, washed and purified to obtain intermediate B. S3: Under nitrogen protection, 1.71 g of intermediate B, 0.23 g of palladium / carbon, and 42 mL of ethanol were added to a container and refluxed in an oil bath at 90 °C for 4 h. Then, 11 mL of hydrated hydrazine was added, and the reflux reaction was continued for 45 min. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, 1.06 g of m-phenylenediamine, 2.71 g of intermediate C, and 85 mL of N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, 1.71 g of isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred at 70 °C for 2 h. Then, 7.1 g of calcium hydroxide was added, and the mixture was stirred for 15 min. The mixture was washed and dried to obtain the color-changing layer material.

[0030] This embodiment discloses a method for fabricating a simple electrochromic device, including the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0031] Example 5: This example discloses a method for preparing a transparent conductive layer material, including the following steps: Q1: 2.63 g of 3-(3-bromomethoxy)4-methylthiophene was added to 20 mL of tetrahydrofuran and stirred until dissolved. Then, 54 mL of 30 wt% trimethylamine aqueous solution was added. The mixture was stirred at room temperature for 48 h and dried by rotary evaporation. Tetrahydrofuran was added and stirred for 45 min. The mixture was filtered, washed with tetrahydrofuran, and dried to obtain compound 1. Q2: 0.26 g of 3-(3-bromomethoxy)4-methylthiophene, 0.35 g of compound 1 and 0.21 g of 3-(2-octyldodecyl)thiophene were added to 34 mL of chloroform, followed by the addition of 1.06 g of ferric chloride. The mixture was heated and stirred at 40 °C for 48 h under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, and added to methanol. Then, 0.07 g of hydrazine hydrate was added, and the mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Add 0.35g of pyridine-3-boronic acid to a mixed solution of 18mL N,N-dimethylformamide and 18mL tetrahydrofuran containing 0.26g of compound 2. Under nitrogen protection, heat and stir at 90℃ for 48h, cool, concentrate, and add dropwise to 115mL tetrahydrofuran for precipitation. Filter, wash with tetrahydrofuran, dissolve in distilled water, dialyze, the molecular cutoff of the dialysis bag is 3500kDa, the dialysis time is 3 days, freeze-dry to obtain a transparent conductive layer material.

[0032] This embodiment discloses a method for preparing a color-changing layer material, including the following steps: S1: Under nitrogen protection, 3.34 g of 5-nitroindole and 40 mL of N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. 1.08 g of sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred for 45 min. Under ice bath conditions, 10 mL of N,N-dimethylformamide containing 2.83 g of 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred for 30 min. The mixture was then reacted in an oil bath at 130 °C for 8 h. After the reaction was completed, the container was cooled, distilled water was added, and the mixture was filtered. The mixture was first washed with N,N-dimethylformamide and then with distilled water. The mixture was dried at 70 °C for 24 h to obtain intermediate A. S2: 0.051g of intermediate A, 0.053g of 3-nitrophenylboronic acid, 0.182g of silver trifluoroacetate, 0.0017g of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and 2.7mL of trifluoroethanol were added to a container and reacted in an oil bath at 90℃ for 8h. After the reaction was completed, the mixture was cooled, 3 drops of triethylamine were added and stirred for 10min, filtered, washed and purified to obtain intermediate B. S3: Under nitrogen protection, 1.93 g of intermediate B, 0.26 g of palladium / carbon, and 52 mL of ethanol were added to a container and refluxed in an oil bath at 90 °C for 4 h. Then, 14 mL of hydrated hydrazine was added, and the reflux reaction was continued for 45 min. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, 1.12 g of m-phenylenediamine, 2.95 g of intermediate C, and 98 mL of N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, 1.87 g of isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred at 70 °C for 2 h. Then, 7.5 g of calcium hydroxide was added, and the mixture was stirred for 15 min. The mixture was washed and dried to obtain the color-changing layer material.

[0033] This embodiment discloses a method for fabricating a simple electrochromic device, including the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.

[0034] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not add 3-(3-bromomethoxy)4-methylthiophene during the preparation of the electrochromic device, and all other conditions remained unchanged.

[0035] Comparative Example 2: Compared with Example 1, Comparative Example 2 did not add 5-nitroindole during the preparation of the electrochromic device, and all other conditions remained unchanged.

[0036] Experimental Example: The samples prepared according to Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests. The color change performance of the samples was tested according to JC / T2631-2021. The samples were placed at 100℃ for 24 hours, and the color and structural changes of the samples were observed. The test results are shown in Table 1. Table 1 As shown in Table 1, the electrochromic devices prepared in Examples 1-5 of this invention exhibit excellent color-changing performance and thermal stability. A comparison between Comparative Example 1 and Examples 1-5 shows that adding 3-(3-bromomethoxy)4-methylthiophene can effectively improve the color-changing performance of the electrochromic devices; a comparison between Comparative Example 2 and Examples 1-5 shows that adding 5-nitroindole can effectively improve the color-changing performance and thermal stability of the electrochromic devices.

[0037] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0038] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A simple electrochromic device, characterized in that, It consists of a transparent conductive layer, a color-changing layer, and an electrolyte. The transparent conductive layer is made of 3-(3-bromomethoxy)4-methylthiophene, 3-(2-octyldodecyl)thiophene, and pyridine-3-boronic acid. The color-changing layer is made of 5-nitroindole, 2-chloropyrimidine, 3-nitrophenylboronic acid, hydrazine hydrate, m-phenylenediamine, and isophthaloyl chloride. The electrolyte layer is made of acrylamide, lithium chloride, and tetramethylethylenediamine.

2. The electrochromic device with a simple structure according to claim 1, characterized in that, The method for preparing the transparent conductive layer material includes the following steps: Q1: 3-(3-bromomethoxy)4-methylthiophene was added to tetrahydrofuran and stirred to dissolve. After that, trimethylamine aqueous solution was added and stirred at room temperature. The mixture was then dried by rotary evaporation. Tetrahydrofuran was added and stirred. The mixture was filtered, washed, and dried to obtain compound 1. Q2: 3-(3-bromomethoxy)4-methylthiophene, compound 1 and 3-(2-octyldodecyl)thiophene were added to chloroform, followed by the addition of ferric chloride. The mixture was heated and stirred under nitrogen protection. After the reaction was completed, the mixture was cooled, dried by rotary evaporation, added to methanol, followed by the addition of hydrazine hydrate. The mixture was stirred thoroughly, filtered, and dried by rotary evaporation to obtain compound 2. Q3: Pyridine-3-boronic acid was added to a mixed solution of N,N-dimethylformamide and tetrahydrofuran containing compound 2. Under nitrogen protection, the mixture was heated and stirred, cooled, concentrated, and then added dropwise to tetrahydrofuran for precipitation. The mixture was filtered, washed, dissolved in distilled water, dialyzed, and freeze-dried to obtain a transparent conductive layer material.

3. The electrochromic device with a simple structure according to claim 2, characterized in that, In Q1, the ratio of 3-(3-bromomethoxy)4-methylthiophene to trimethylamine aqueous solution is (2.12-2.77) g: (42-58) mL, the mass fraction of trimethylamine aqueous solution is 30 wt%, the stirring reaction time is 40-50 h, tetrahydrofuran is added and stirred for 30-45 min, and then washed with tetrahydrofuran.

4. The electrochromic device with a simplified structure according to claim 2, characterized in that, In Q2, the ratio of 3-(3-bromomethoxy)4-methylthiophene, compound 1, 3-(2-octyldodecyl)thiophene, chloroform, ferric chloride, and hydrazine hydrate is (0.21-0.27) g : (0.24-0.38) g : (0.13-0.25) g : (28-35) mL : (0.93-1.08) g : (0.05-0.08) g. The heating and stirring reaction temperature is 30-40℃, and the reaction time is 42-54 h.

5. The electrochromic device with a simplified structure according to claim 2, characterized in that, In Q3, the ratio of pyridine-3-boronic acid, compound 2, N,N-dimethylformamide, tetrahydrofuran, and the amount of tetrahydrofuran added is (0.29-0.38) g : (0.21-0.28) g : (10-20) mL : (10-20) mL : (90-110) mL. The heating and stirring temperature is 90-95℃, the stirring time is 42-54 h, and the mixture is washed with tetrahydrofuran. During dialysis, the molecular cutoff of the dialysis bag is 3500 kDa, and the dialysis time is 2-4 days.

6. The electrochromic device with a simple structure according to claim 1, characterized in that, The method for preparing the color-changing layer material includes the following steps: S1: Under nitrogen protection, 5-nitroindole and N,N-dimethylformamide were added to a container and stirred until dissolved. The container was then cooled in an ice bath. Sodium hydride was added in portions. After the addition was complete, the container was heated to room temperature and stirred. Under ice bath conditions, N,N-dimethylformamide containing 2-chloropyrimidine was added to the container. After the addition was complete, the container was heated and stirred. The mixture was then reacted in an oil bath. After the reaction was complete, the container was cooled, distilled water was added, and the mixture was filtered, washed, and dried to obtain intermediate A. S2: Add intermediate A, 3-nitrophenylboronic acid, silver trifluoroacetate, dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and trifluoroethanol to a container and react in an oil bath. After the reaction is complete, cool, add triethylamine and stir, filter, wash and purify to obtain intermediate B. S3: Under nitrogen protection, intermediate B, palladium / carbon, and ethanol were added to a container and refluxed in an oil bath. Then, hydrated hydrazine was added, and the reflux reaction continued. After the reaction was completed, the mixture was filtered, washed, concentrated by rotary evaporation, dried, filtered again, and dried by rotary evaporation to obtain intermediate C. Under nitrogen protection, m-phenylenediamine, intermediate C, and N,N-dimethylacetamide were added to a container and stirred to dissolve. Then, isophthaloyl chloride was added under ice bath conditions. After the addition was complete, the mixture was heated and stirred to react. Subsequently, calcium hydroxide was added, and the mixture was stirred, washed, and dried to obtain the color-changing layer material.

7. The electrochromic device with a simplified structure according to claim 6, characterized in that, In S1, the ratio of 5-nitroindole, sodium hydride, and 2-chloropyrimidine is (3.12-3.38) g : (1.01-1.12) g : (2.43-2.97) g. The stirring time at room temperature is 30-45 min, the stirring time at elevated temperature is 30-45 min, the oil bath reaction temperature is 120-140℃, and the reaction time is 6-8 h. The mixture is first washed with N,N-dimethylformamide, then washed with distilled water, and the drying temperature is 60-70℃ for 20-24 h.

8. The electrochromic device with a simplified structure according to claim 6, characterized in that, In S2, the ratio of intermediate A, 3-nitrophenylboronic acid, silver trifluoroacetate, dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer and trifluoroethanol is (0.034-0.055) g : (0.042-0.055) g : (0.172-0.186) g : (0.0015-0.0018) : (2-3) mL. The oil bath reaction temperature is 80-90℃, the reaction time is 6-9 h, and the stirring time is 5-10 min.

9. The electrochromic device with a simplified structure according to claim 6, characterized in that, In S3, the ratio of intermediate B, palladium / carbon, ethanol, and hydrated hydrazine is (1.63-2.01) g : (0.21-0.28) g : (45-55) mL : (10-15) mL, the oil bath reflux reaction temperature is 80-90℃, the reaction time is 3-5 h, and the reflux reaction time is continued for 30-45 min; the ratio of m-phenylenediamine, intermediate C, N,N-dimethylacetamide, isophthaloyl chloride, and calcium hydroxide is (1.05-1.13) g : (2.63-3.04) g : (80-102) mL : (1.62-1.93) g : (6.8-7.6) g, the heating and stirring reaction temperature is 60-70℃, the reaction time is 1-2 h, and the stirring time is continued for 10-20 min.

10. A simplified electrochromic device according to claims 1-9, characterized in that, Its preparation method includes the following steps: Step 1: Add acrylamide and lithium chloride to deionized water, then add N,N-methylenebisacrylamide, tetramethylethylenediamine and ammonium persulfate in sequence. After stirring at room temperature, pour into a mold, flatten, and remove to obtain the electrolyte layer. Step 2: Coat the color-changing layer material evenly onto the surface of the electrolyte layer, then add a transparent conductive layer on the surface of the color-changing layer, flatten it, and dry it to obtain a simple electrochromic device.