Electrochromic ion storage layer thin film and method of making same

Abstract

This invention discloses a method for preparing an electrochromic ion storage layer thin film, comprising the following steps: S1: reacting terephthalaldehyde or a terephthalaldehyde derivative with 2-acetylpyridine or a 2-acetylpyridine derivative to generate 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene or a derivative thereof; then reacting it with ammonium acetate to obtain an organic ligand; reacting it with RuCl2(DMSO)4 to obtain a metal supramolecular polymer; S2: mixing it uniformly with a solvent and dimethylformamide to obtain an electrochemical deposition precursor solution; S3: depositing it at a constant potential via electrochemical deposition to obtain the electrochromic ion storage layer thin film. The thin film prepared by this invention not only has advantages such as fast response speed, high coloring efficiency, and wide optical modulation range, but also has good cycling stability.

Description

Technical Field

[0001] This invention relates to the technical field of thin films, and more particularly to an electrochromic ion storage layer thin film and its preparation method. Background Technology

[0002] Electrochromism is a phenomenon in which the optical properties (transmittance, reflectance, and absorbance) of a material reversibly change with the polarity and intensity of an applied electric field. Electrochromic devices have enormous commercial application potential in fields such as smart windows, anti-glare rearview mirrors, information displays, and flexible wearable fabrics.

[0003] A typical electrochromic device usually consists of two transparent conductive layers, an electrochromic layer, an electrolyte layer, and a counter electrode layer. Complementary electrochromic devices, typically composed of cathode and anode electrochromic materials, generally exhibit excellent electrochromic performance. Among these, tungsten oxide (WO3) is highly favored as the most promising cathode electrochromic material. For the counter electrode (ion storage layer) material of tungsten oxide, charge complementarity needs to be achieved, matching both the charge storage capacity and charge storage / release rate (i.e., the electrochromic response speed) of tungsten oxide. Simultaneously, the electrochemical window of the ion storage layer must be consistent with that of the electrochromic layer. Furthermore, while the optical contrast of the ion storage layer is not overly critical, its color fading needs to be complementary to that of the electrochromic layer. Therefore, when selecting materials for the electrode ion storage layer, it is necessary to meet conditions such as high charge storage capacity, fast electrochromic response speed, good cycle stability, and wide optical modulation range. However, the materials involved in existing research are mostly transition metal oxides such as nickel oxide (NiO) and manganese oxide (MnO2) and organic materials such as polyaniline. These traditional materials have limited charge storage capacity, slow response speed, and poor cycle stability. For example, the charge capacity of nickel oxide and manganese oxide is only 3~6 mC / cm2, and the fading time is 10~15 s. They have limited charge storage capacity and slow electrochromic response speed. After 1000 charge-discharge cycles, the charge capacity of polyaniline can only be maintained at 50%, which is difficult to meet the long cycle stability requirements of ion storage layer films. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention provides a method for preparing an electrochromic ion storage layer thin film to solve the problem that existing electrochromic ion storage layers cannot simultaneously achieve excellent performance such as fast response speed, high coloring efficiency, wide optical modulation range and good cycle stability.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing an electrochromic ion storage layer thin film, the method comprising the following steps:

[0007] Synthesis of S1 metal supramolecular polymer: Terephthalaldehyde or its derivatives are used as the first raw material, and 2-acetylpyridine or its derivatives are used as the second raw material. The two react to generate 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene or its derivatives. Then, the 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene or its derivatives are reacted with ammonium acetate to obtain the organic ligand 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene or its derivatives. Finally, the 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene or its derivatives are reacted with RuCl2(DMSO)4 to obtain the metal supramolecular polymer.

[0008] Preparation of S2 precursor solution: The metal supramolecular polymer obtained in step S1 is dissolved in a solvent, and dimethylformamide is added and stirred until homogeneous to obtain an electrochemical deposition precursor solution; Dimethylformamide is selected in this application to facilitate the metal supramolecular polymer in the electrochemical deposition precursor solution to form a film under electrochemical action, thereby forming the high-performance electrochromic ion storage layer thin film of this application.

[0009] S3 Thin film preparation: The precursor solution obtained in step S2 is deposited by electrochemical deposition at a constant potential, and the electrochromic ion storage layer thin film is obtained after drying.

[0010] Preferably, the terephthalaldehyde derivative is at least one selected from tetrafluoroterephthalaldehyde, 2,5-dichloroterephthalaldehyde, 2,5-diethoxyterephthalaldehyde, and 2,5-dimethylterephthalaldehyde.

[0011] Preferably, the 2-acetylpyridine derivative is at least one of 2-acetyl-6-methoxypyridine, 2-acetyl-4-methylpyridine, and 2-acetyl-6-methylpyridine.

[0012] Preferably, the first raw material and the second raw material are reacted in a strong alkaline solution with a mass concentration of 10-30%.

[0013] Preferably, the strong alkaline solution is a potassium hydroxide solution or a sodium hydroxide solution.

[0014] Preferably, the reaction of 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene or its derivative with RuCl2(DMSO)4 is carried out under inert gas protection in a solvent by heating and reflux, and the molar ratio of 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene or its derivative with RuCl2(DMSO)4 is 1:1.

[0015] Preferably, the electrochemical deposition uses a transparent conductive glass electrode as the working electrode and a platinum sheet as the counter electrode, with a constant potential of 6.0–10.0 V and a deposition time of 5–10 min.

[0016] Another aspect of the present invention is to provide an electrochromic ion storage layer thin film, which is prepared by the electrochromic ion storage layer thin film preparation method described above.

[0017] Preferably, the electrochromic ion storage layer film has a high coloring efficiency of greater than 90 cm2C-1 in the 622-760 nm red light band and an optical modulation range of greater than 70%.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] The electrochromic ion storage layer thin film prepared by this invention introduces an organic-inorganic hybrid metal-supramolecular polymer as the ion storage layer, thereby improving the electrochromic and electrochemical performance of the ion storage layer material. It not only possesses a fast electrochromic response speed but also exhibits superior performance advantages in the 622–760 nm red light band, including high coloring efficiency and a wide optical modulation range; thus meeting the performance requirements of specific applications such as intelligent building windows, automotive sunroofs, and information displays.

[0020] The present invention discloses a method for preparing an electrochromic ion storage layer thin film, which provides a simple and low-cost method for preparing an organic-inorganic hybrid composite electrochromic thin film with good cycle stability, thus meeting the requirements for long-term use of electrochromic ion storage layer thin films.

[0021] The method for preparing the electrochromic ion storage layer thin film of the present invention overcomes the problems of uneven or aggregated active materials that usually occur in electrochromic thin films formed by traditional spin coating and other methods. Furthermore, no organic binder needs to be added during the film formation process, so it does not hinder the movement of charges inside the film, thereby improving the electrochromic performance of the film. Attached Figure Description

[0022] Figure 1 a is a SEM image of polyRu / ITO on a glass substrate in Embodiment 1 of the present invention.

[0023] Figure 1 b is the FTIR spectrum of polyRu / ITO on the glass substrate in Embodiment 1 of the present invention.

[0024] Figure 1 c is the XPS spectrum of Ru 3p in Embodiment 1 of the present invention.

[0025] Figure 1d is the XPS spectrum of N 1s in Embodiment 1 of the present invention.

[0026] Figure 2 a is the polyRu film of Embodiment 1 of the present invention ( Figure 2 a to Figure 2 f(all using LiClO4-MeCN electrolyte) cyclic voltammetry (CV) at different scan rates.

[0027] Figure 2 b is a power-law relationship graph between the scanning rate and the peak current in Embodiment 1 of the present invention.

[0028] Figure 2 c is a capacitance retention diagram of the thin film when the current density is 0.3 mA∙cm⁻² in Example 1 of the present invention.

[0029] Figure 2 d represents the transmission spectrum of the thin film in Example 1 of the present invention under different voltages.

[0030] Figure 2 e is a graph showing the proportion of diffusion-controlled capacitance to total capacitance in the in-situ transmission spectrum of the thin film at λ700nm in Embodiment 1 of the present invention.

[0031] Figure 2 f represents the coloring efficiency of the thin film in Example 1 of this invention at λ700nm.

[0032] Figure 3 a is the polyRu film of Embodiment 1 of the present invention ( Figure 3 a to Figure 3 c uses Bu4NClO4-MeCN electrolyte) at different scan rates for cyclic voltammetry (CV).

[0033] Figure 3 b is a power-law relationship graph of the scan rate and peak current of the polyRu thin film in Bu4NClO4-MeCN electrolyte in Example 1 of the present invention.

[0034] Figure 3 c represents the ratio of capacitance control to diffusion control of the polyRu thin film in Example 1 of this invention at different scan rates.

[0035] Figure 4 a is the CV curve of the polyRu film prepared by spraying process in Comparative Example 3 of the present invention after 300 cycles.

[0036] Figure 4 b is the CV curve of the polyRu film prepared by electrochemical deposition process in Example 1 of the present invention after 300 cycles. Detailed Implementation

[0037] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0038] Example 1

[0039] The method for preparing the electrochromic ion storage layer thin film in this embodiment includes the following steps:

[0040] Synthesis of S1 metal supramolecular polymer: First, terephthalaldehyde was selected as the first raw material and 2-acetylpyridine as the second raw material. To a 200 ml methanol solution of terephthalaldehyde (2.68 g, 0.02 mol), 10.89 g of 2-acetylpyridine (0.09 mol) and a 20% potassium hydroxide strong alkali solution (5.04 g potassium hydroxide, 20 ml deionized water) were added and stirred until homogeneous. After reacting at room temperature for 1 day, the temperature was raised to 55 °C and the reaction continued for another day. After the reaction was completed, solid particles were obtained by vacuum filtration, washed three times each with deionized water and methanol, and dried under vacuum to obtain the product 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene. Next, 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene (8.1 g, 0.014 mol) was mixed with ammonium acetate (40.5 g, 0.53 mol) and 400 ml of ethanol and stirred for 4 days at 60 °C. After the reaction was completed, a pale yellow solid was obtained by vacuum filtration and washed twice with deionized water and ethanol, respectively. After drying, the pale yellow solid was mixed with glacial acetic acid, heated and stirred to dissolve, and then the above mixed solution was cooled to 15 °C in a cold water bath. The solid precipitated after filtration and recrystallization was collected, washed three times with ethanol, and dried under vacuum to obtain the organic ligand 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene. Finally, under nitrogen protection, 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene and RuCl2(DMSO)4 (CAS No.: 72904-47-3) in the same molar ratio were refluxed in ethylene glycol for 24 h. After the reaction solution was cooled to room temperature, a large amount of tetrahydrofuran was added until the solution became colorless. After standing, the solution was filtered to collect the red precipitate polymer, washed three times with tetrahydrofuran, and dried under vacuum to obtain the target product, the metal supramolecular polymer, abbreviated as polyRu. The synthetic route of 1,4-bis(2,2′:6′,2′′-terpyridin-4′-yl)benzene is shown below.

[0041] .

[0042] Preparation of S2 precursor solution: Dissolve 100 mg of the metal supramolecular polymer obtained in step S1 in 25 mL of methanol solvent, add 25 mL of dimethylformamide, stir and mix evenly to obtain the electrochemical deposition precursor solution.

[0043] S3 Thin Film Preparation: The precursor solution obtained in step S2 is deposited by electrochemical deposition at a constant potential. After drying, the electrochromic ion storage layer thin film, abbreviated as polyRu thin film, is obtained. The electrochemical deposition uses a transparent conductive glass electrode as the working electrode and a platinum sheet as the counter electrode, with a constant potential of 6.0–10.0 V and a deposition time of 5–10 min.

[0044] The electrochromic ion storage layer film prepared in this embodiment was subjected to performance testing, and the results are as follows:

[0045] Figure 1 SEM images of the polyRu film showed that it was relatively uniform and dense, without obvious damage or defects, with good film-substrate adhesion and a film thickness of 2.18 μm. Figure 1 The FTIR spectra of particles and films in b show that, apart from the ethylene glycol peak remaining during particle washing, the infrared characteristic peaks of the films and particles are no different. Figure 1 c and Figure 1 XPS fine spectra of Ru and N in d were quantitatively analyzed to show that the atomic ratio of Ru to N was 1:6.5, which is consistent with the atomic ratio of the original particles within an acceptable error range. Therefore, it is shown that polyRu films were successfully prepared by electrochemical deposition.

[0046] Figure 2 Figure a shows the cyclic voltammetry curves of the polyRu thin film (hereinafter the same) in LiClO4-MeCN electrolyte at different scan rates. It can be seen that the redox peaks of the film exhibit good reversibility in the voltage range of 0-1.8 V. For example... Figure 2 As shown in b, the b-values ​​of the oxidation and reduction peaks, calculated using cyclic voltammetry, are 0.63 and 0.64, respectively. Both have R² values ​​close to 1, indicating reliable b-value results. This suggests that the oxidation and reduction peaks are the result of a combination of capacitance and diffusion behavior. Furthermore, the high overlap of the b-values ​​of the oxidation and reduction peaks further demonstrates the excellent reversibility of the electrochemical reaction, which is one of the reasons for the highly stable electrochromic phenomenon of the polyRu film. The cyclic stability of the film was tested using constant current charge-discharge, such as... Figure 2 As shown in Figure c, after 5000 charge-discharge cycles, the film capacitor still retains 76% of its capacitance, demonstrating excellent cycle stability. Figure 2 d represents the transmission spectrum of the polyRu film at different voltages. It can be seen that the film has an optical modulation range of up to 72.2% in the voltage range of 0-1.8V. Figure 2 The results indicate that the polyRu film exhibits a fast response speed under step voltages of 0 V / 1.8 V, with both the color-changing and fading times being 2.7 s. Furthermore... Figure 2 f indicates that the polyRu film exhibits a high coloring efficiency of 91.24 cm²∙C⁻¹ at 700 nm. This demonstrates that the polyRu film possesses excellent electrochromic properties.

[0047] Figure 3 a represents the cyclic voltammetry curves of the polyRu film (hereinafter the same) in the Bu4NClO4-MeCN electrolyte at different scan rates. It can be seen that the redox peaks in the electrochemical process of the film also have good reversibility. Figure 3 The b-values ​​of the oxidation and reduction peaks, calculated using cyclic voltammetry, are 0.65 and 0.64, respectively, almost identical to those of the Li+-based electrolyte. This indicates that the electrochemical reactions of the polyRu film under different electrolytes are highly reversible. This also demonstrates that the polyRu film exhibits excellent cycling stability in Bu4NClO4-MeCN electrolyte. Figure 3 c represents the capacitance and diffusion ratios during the electrochemical process of the polyRu thin film at different scan rates. It can be seen that the electrochemical process of the film is mainly caused by capacitive behavior (including surface, near-surface, and interlayer pseudocapacitances), thus resulting in a fast response speed. This phenomenon is also related to... Figure 2 The consistent performance of polyRu films in eLi+-based electrolytes indicates that polyRu films exhibit high performance and high stability in different electrolytes.

[0048] Example 2

[0049] The electrochromic ion storage layer film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that tetrafluoroterephthalaldehyde is used as the first raw material and 2-acetyl-6-methoxypyridine is used as the second raw material.

[0050] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 71.5% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.6s; in addition, it has a high coloring efficiency of 95.32cm2∙C-1 at 700nm.

[0051] Example 3

[0052] The electrochromic ion storage layer film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that 2,5-dichloroterephthalaldehyde is used as the first raw material and 2-acetyl-6-methoxypyridine is used as the second raw material.

[0053] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 73.2% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.7s; in addition, it has a high coloring efficiency of 94.61cm2∙C-1 at 700nm.

[0054] Example 4

[0055] The electrochromic ion storage layer thin film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that 2,5-diethoxyterephthalaldehyde is used as the first raw material and 2-acetyl-4-methylpyridine is used as the second raw material.

[0056] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 72.1% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.6s; in addition, it has a high coloring efficiency of 96.11cm2∙C-1 at 700nm.

[0057] Example 5

[0058] The electrochromic ion storage layer film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that 2,5-dimethylterephthalaldehyde is used as the first raw material and 2-acetyl-6-methylpyridine is used as the second raw material.

[0059] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 71.8% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.8s; in addition, it has a high coloring efficiency of 93.86cm2∙C-1 at 700nm.

[0060] Example 6

[0061] The electrochromic ion storage layer film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that terephthalaldehyde is used as the first raw material and 2-acetyl-6-methoxypyridine is used as the second raw material.

[0062] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 72.8% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.5s; in addition, it has a high coloring efficiency of 94.02cm2∙C-1 at 700nm.

[0063] Example 7

[0064] The electrochromic ion storage layer film of this embodiment is prepared in a basically the same way as in Example 1. The main difference is that tetrafluoroterephthalaldehyde is used as the first raw material and 2-acetylpyridine is used as the second raw material.

[0065] The electrochromic ion storage layer thin film prepared in this embodiment was subjected to performance testing. The results showed that the thin film of this embodiment has an optical modulation range of up to 72.3% in the voltage range of 0-1.8V; it has a fast response speed at step voltages of 0 V / 1.8 V, with a coloring and fading time of 2.7s; in addition, it has a high coloring efficiency of 95.88cm2∙C-1 at 700nm.

[0066] Comparative Example 1

[0067] The preparation method of this comparative electrochromic ion storage layer film is basically the same as that of Example 1. The main difference is that Cu(CH3COO) is used instead of RuCl2(DMSO)4.

[0068] The electrochromic ion storage layer thin film prepared in this comparative example was subjected to performance testing. The results showed that the film in this comparative example had only 20% optical modulation range in the voltage range of 0-1.8V; it had a high coloring efficiency of 260 cm2∙C-1 at 580 nm, but only 42.15 cm2∙C-1 at 700 nm.

[0069] Comparative Example 2

[0070] The preparation method of this comparative electrochromic ion storage layer film is basically the same as that of Example 1. The main difference is that (NH4)2OsCl6 is used instead of RuCl2(DMSO)4.

[0071] The electrochromic ion storage layer thin film prepared in this comparative example was subjected to performance testing. The results showed that the film in this comparative example had only 13% optical modulation range in the voltage range of 0-1.8V; it had a high coloring efficiency of 301 cm2∙C-1 at 515 nm, but only 58.62 cm2∙C-1 at 700 nm.

[0072] Comparative Example 3

[0073] The preparation method of this comparative electrochromic ion storage layer film is basically the same as that of Example 1. The main difference is that the deposition steps S2 and S3 adopt a spraying process (non-electrochemical deposition method). Specifically, the metal supramolecular polymer (abbreviated as polyRu) obtained in step S1 is dissolved in methanol to obtain an ink solution (2 mg / mL). The solution is filtered with a microporous membrane (polyvinylidene fluoride, 0.45 μm) to remove trace amounts of insoluble matter. Then, the ink solution is sprayed onto the same transparent conductive glass as in Example 1 to obtain a red polyRu film.

[0074] The electrochromic ion storage layer films prepared in this comparative example and in Example 1 were compared and tested for performance. Figure 4 a and Figure 4 As shown in b, after 300 CV cycles, the CV curve of the polyRu film prepared by the spraying method showed obvious degradation; while the shape of the CV curve of the film prepared by the electrochemical deposition method did not change significantly, indicating that the polyRu film prepared by electrochemical deposition has good electrochemical stability.

[0075] Therefore, it is evident that this invention patent has significant advantages over currently used technologies. The basic principles, main features, and advantages of this invention have been shown and described above. Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for preparing an electrochromic ion storage layer thin film, characterized in that, The preparation method includes the following steps: Synthesis of S1 metal supramolecular polymer: Terephthalaldehyde or its derivatives are used as the first raw material, and 2-acetylpyridine or its derivatives are used as the second raw material. The two react to generate 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene or its derivatives. Then, the 1,4-bis[1,5-dioxo-1,5-bis(2-pyridyl)pentan-3-yl]benzene or its derivatives are reacted with ammonium acetate to obtain the organic ligand 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene or its derivatives. Finally, the 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene or its derivatives are reacted with RuCl2(DMSO)4 to obtain the metal supramolecular polymer. Preparation of S2 precursor solution: Dissolve the metal supramolecular polymer obtained in step S1 in a solvent, add dimethylformamide, stir and mix evenly to obtain an electrochemical deposition precursor solution. S3 Thin film preparation: The precursor solution obtained in step S2 is deposited by electrochemical deposition at a constant potential, and the electrochromic ion storage layer thin film is obtained after drying. The electrochemical deposition uses a transparent conductive glass electrode as the working electrode and a platinum sheet as the counter electrode, with a constant potential of 6.0–10.0 V and a deposition time of 5–10 min; the electrochromic ion storage layer film exhibits a wavelength greater than 90 cm⁻¹ in the 622–760 nm red light band. 2 C -1 It has high coloring efficiency and an optical modulation range of more than 70%.

2. The method for preparing the electrochromic ion storage layer thin film as described in claim 1, characterized in that, The terephthalaldehyde derivative is at least one of tetrafluoroterephthalaldehyde, 2,5-dichloroterephthalaldehyde, 2,5-diethoxyterephthalaldehyde, and 2,5-dimethylterephthalaldehyde.

3. The method for preparing the electrochromic ion storage layer thin film as described in claim 1, characterized in that, The 2-acetylpyridine derivative is at least one of 2-acetyl-6-methoxypyridine, 2-acetyl-4-methylpyridine, and 2-acetyl-6-methylpyridine.

4. The method for preparing the electrochromic ion storage layer thin film as described in claim 1, characterized in that, The first and second raw materials react in a strong alkaline solution with a mass concentration of 10-30%.

5. The method for preparing the electrochromic ion storage layer thin film as described in claim 4, characterized in that, The strong alkaline solution is a potassium hydroxide solution or a sodium hydroxide solution.

6. The method for preparing the electrochromic ion storage layer thin film as described in claim 1, characterized in that, The reaction of 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene or its derivative with RuCl2(DMSO)4 is carried out under inert gas protection in a solvent by heating and reflux, and the molar ratio of 1,4-bis(2,2′:6′,2″-terpyridin-4′-yl)benzene or its derivative with RuCl2(DMSO)4 is 1:

1.

7. An electrochromic ion storage layer thin film, characterized in that, The electrochromic ion storage layer thin film is prepared by the preparation method of the electrochromic ion storage layer thin film as described in any one of claims 1 to 6.

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