Metal electrodeposition color-changing device as well as preparation method and application thereof

Abstract

The invention provides a metal electrodeposition color-changing device and a preparation method and application thereof, and belongs to the technical field of photoelectrode materials. The invention provides a metal electrodeposition color changing device which comprises a first substrate, a first transparent conductive metal oxide layer, an electrolyte layer, a conductive polymer film, a second transparent conductive metal oxide layer and a second substrate which are sequentially stacked, and the electrolyte layer contains metal ions. According to the invention, the conductive polymer film with excellent redox reversibility is introduced into the structure of the related technology as the counter electrode (ion storage layer), so that the working voltage of the metal electrodeposition color-changing device is effectively reduced, and meanwhile, good adhesive force can be formed between the conductive polymer film and the second transparent conductive metal oxide; the structural stability and the electrochemical cycle stability of the metal electrodeposition color-changing device are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photoelectrode materials, and in particular to a metal electrodeposition color-changing device and a preparation method and application thereof. Background Art

[0002] Electrochromic materials and devices have great application value in the fields of panoramic dimming skylights for new energy vehicles, intelligent windows for building light and heat regulation, non-luminous electronic displays, etc., and have attracted much attention in recent years. At present, the most widely used electrochromic materials, such as inorganic tungsten oxide, organic small molecule viologen, and organic conductive polymer polythiophene materials, are mostly based on the redox regulation of materials to achieve the regulation of their structural changes to achieve optical properties. They generally require complex structural design and long-term synthesis processes, and have high R&D costs. In recent years, electrochromic systems based on the principle of reversible metal electrodeposition have received widespread attention. The electrochromic principle of this type of system is: the deposition and dissolution of metal films are regulated by electric fields, and the optical transmittance difference between metal films and metal ion solutions is used to achieve reversible regulation of optical properties by electric fields. Its raw materials are easy to obtain, no synthesis is required, and it has a low cost. At the same time, due to the special optical properties of metal films, it exhibits specific intelligent color-changing characteristics of neutral colors, which is of great value in new electrochromic application fields.

[0003] Currently, the device structure of most metal electrodeposition includes a substrate, a transparent conductive metal oxide layer, an electrolyte layer (including metal ions), a transparent conductive metal oxide layer (as a counter electrode) and a substrate. Using a transparent metal oxide layer as a counter electrode has a relatively stable device structure and is easy to package. However, due to the lack of suitable ion storage layer (counter electrode) materials, the operating voltage is generally high (usually greater than 2V). Summary of the invention

[0004] In view of this, the object of the present invention is to provide a metal electrodeposition color-changing device and a preparation method and application thereof. The metal electrodeposition color-changing device provided by the present invention has a low operating voltage.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The invention provides a metal electrodeposition color-changing device, comprising a first substrate, a first transparent conductive metal oxide layer, an electrolyte layer, a conductive polymer film, a second transparent conductive metal oxide layer and a second substrate which are stacked in sequence, wherein the electrolyte layer contains metal ions.

[0007] Preferably, the material of the conductive polymer film includes one or more of polyaniline, polythiophene, polypyrrole, polyparaphenylene, polyparaphenylene and polythiophene derivatives.

[0008] Preferably, the polythiophene derivative comprises poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) and / or poly[[3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6,8-diyl]].

[0009] Preferably, the thickness of the conductive polymer film is 50 nm to 2 μm.

[0010] Preferably, the electrolyte layer is an aqueous solution or an electrochromic hydrogel.

[0011] Preferably, the metal ions include one or more of copper ions, zinc ions, bismuth ions and silver ions.

[0012] Preferably, the electrochromic hydrogel is prepared by a method comprising the following steps:

[0013] mixing a soluble metal salt, an electrolyte and water to obtain a metal electrodeposition aqueous solution;

[0014] The metal electrodeposition aqueous solution is poured into the hydrogel to obtain the electrochromic hydrogel.

[0015] Preferably, the hydrogel comprises one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyethylene oxide and polyhydroxyethyl methacrylate.

[0016] The present invention also provides a method for preparing the metal electrodeposition color-changing device described in the above technical solution, comprising the following steps:

[0017] Depositing on the surface of the first substrate to obtain a first transparent conductive metal oxide layer;

[0018] Depositing on the surface of the second substrate to obtain a second transparent conductive metal oxide layer;

[0019] coating a conductive polymer dispersion on the surface of the second transparent conductive metal oxide layer to form a film to obtain a conductive polymer film;

[0020] A spacing groove is placed on the surface of the first transparent conductive metal oxide layer, and then the spacing groove is filled with electrolyte material, and then covered with the conductive polymer film to obtain the metal electrodeposition color-changing device.

[0021] The present invention also provides the application of the metal electrodeposition color-changing device described in the above technical solution in the fields of anti-glare rearview mirrors, building curtain walls, automobile glass, electronic tags, electronic billboards, smart windows and reflective displays.

[0022] The invention provides a metal electrodeposition color-changing device, comprising a first substrate, a first transparent conductive metal oxide layer, an electrolyte layer, a conductive polymer film, a second transparent conductive metal oxide layer and a second substrate which are stacked in sequence, wherein the electrolyte layer contains metal ions.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] Figure 2 is a schematic diagram of the structure of a metal electrodeposition device in the related art, Figure 1 This is a schematic diagram of the structure of the metal electrodeposition color-changing device of the present invention. The present invention effectively reduces the operating voltage of the metal electrodeposition color-changing device by introducing a conductive polymer film with excellent redox reversibility as a counter electrode (ion storage layer) in the structure of the related technology. At the same time, since good adhesion can be formed between the conductive polymer film and the second transparent conductive metal oxide, the structural stability and electrochemical cycle stability of the metal electrodeposition color-changing device are improved.

[0025] Furthermore, the present invention limits the electrolyte layer to an aqueous solution or an electrochromic hydrogel. The electrochromic hydrogel can be used as both an electrolyte and an electrochromic material. It can control the reversible switching of optical transmittance by voltage in a non-liquid state, thereby achieving efficient regulation of optical properties and stable color switching.

[0026] The present invention also provides a method for preparing the metal electrodeposition color-changing device described in the above technical solution. The preparation method of the present invention is simple to operate, easy to realize industrial application, and low in cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic structural diagram of the metal electrodeposition color-changing device of the present invention;

[0028] Figure 2 It is a schematic diagram of the structure of a metal electrodeposition device in the related art;

[0029] Figure 3 This is a schematic diagram of the color switching state of the metal electrodeposition color-changing device of Example 1;

[0030] Figure 4 The UV-visible-near infrared transmission spectra of the metal electrodeposition color-changing device of Example 1 at different voltages;

[0031] Figure 5 The cycle stability of the metal electrodeposition color-changing device of Example 1;

[0032] Figure 6 This is a schematic diagram of the color switching state of the metal electrodeposition color-changing device of Example 2;

[0033] Figure 7 The UV-visible-near infrared transmission spectra of the metal electrodeposition color-changing device of Example 2 at different voltages;

[0034] Figure 8 The cycle stability of the metal electrodeposition color-changing device of Example 2;

[0035] Fig. 9 A schematic diagram of the color switching state and an optical transmittance curve of the metal electrodeposition device prepared in Example 3;

[0036] Fig.10 The effect of the metal electrodeposition device prepared in Example 3 on the electrochromic response capability;

[0037] Fig.11 Schematic diagram of the color switching state of the metal electrodeposition device of Comparative Example 1;

[0038] Fig.12 This is the cycle stability of the metal electrodeposition device of Comparative Example 1. DETAILED DESCRIPTION

[0039] The invention provides a metal electrodeposition color-changing device, comprising a first substrate, a first transparent conductive metal oxide layer, an electrolyte layer, a conductive polymer film, a second transparent conductive metal oxide layer and a second substrate which are stacked in sequence, wherein the electrolyte layer contains metal ions.

[0040] Figure 1 The schematic diagram of the structure of the metal electrodeposition color changing device of the present invention is shown below. Figure 1 The structure of the metal electrodeposition color-changing device of the present invention is described.

[0041] The metal electrodeposition color-changing device of the present invention includes a first substrate and a second substrate.

[0042] In the present invention, the first substrate and the second substrate are independently preferably glass or a polymer film, and the polymer film is preferably polyethylene terephthalate (PET), polyurethane (PU) and polyimide (PI). The present invention has no particular limitation on the thickness of the first substrate and the second substrate, and parameters well known to those skilled in the art can be used.

[0043] The metal electrodeposition color-changing device of the present invention comprises a first transparent conductive metal oxide layer and a second transparent conductive metal oxide layer.

[0044] In the present invention, the first transparent conductive metal oxide layer and the second transparent conductive metal oxide layer are independently indium tin oxide (ITO), aluminum-doped zinc oxide (AZO) or fluorine-doped tin dioxide (FTO). The present invention has no special limitation on the thickness of the first transparent conductive metal oxide layer and the second transparent conductive metal oxide layer, and parameters well known to those skilled in the art can be used.

[0045] The metal electrodeposition color-changing device of the present invention includes a conductive polymer film. The present invention uses a conductive polymer film with excellent redox reversibility as a counter electrode (ion storage layer), which effectively reduces the operating voltage of the metal electrodeposition color-changing device. At the same time, since good adhesion can be formed between the conductive polymer film and the second transparent conductive metal oxide, the structural stability and electrochemical cycle stability of the metal electrodeposition color-changing device are improved.

[0046] In the present invention, the material of the conductive polymer film preferably includes one or more of polyaniline, polythiophene, polypyrrole, polyparaphenylene, polyparaphenylene and polythiophene derivatives.

[0047] In the present invention, the polythiophene derivative preferably includes poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) ((PEDOT:PSS)) and / or poly[[3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6,8-diyl]].

[0048] In the present invention, the thickness of the conductive polymer film is preferably 50nm to 2μm, specifically 0.05, 0.065, 0.1, 0.15, 0.25, 0.3, 0.5, 0.8, 1 or 2μm. The thickness of the conductive polymer film is not less than 50nm to ensure that the polymer film has a sufficient amount for electrochemical redox reaction. The thickness of the conductive polymer film is not more than 2μm to avoid the initial light transmittance being low due to excessive thickness of the film, thereby limiting the improvement of the electrochromic optical modulation performance.

[0049] The metal electrodeposition color-changing device of the present invention comprises an electrolyte layer containing metal ions.

[0050] In the present invention, the metal ions preferably include one or more of copper ions, zinc ions, bismuth ions and silver ions.

[0051] In the present invention, the concentration of metal ions in the electrolyte layer is preferably 0.1 to 100 mM, specifically 0.1, 1, 10, 20, 40, 60, 80 or 100 mM. The concentration of the metal ions is not less than 0.1 mM to ensure that there is a sufficient amount of metal ions for electrochemical redox reaction. The concentration of the metal ions is not more than 100 mM because it is limited by its solubility. At the same time, too high a concentration of metal ions can easily lead to some electrochemical side reactions, affecting the electrochromic performance.

[0052] In the present invention, the electrolyte layer is preferably an aqueous solution or an electrochromic hydrogel.

[0053] In the present invention, the aqueous solution is preferably prepared by a method comprising the following steps: mixing a soluble metal salt, an electrolyte and water to obtain the aqueous solution.

[0054] The present invention has no particular limitation on the specific type of the soluble metal salt, and raw materials familiar to those skilled in the art may be used.

[0055] In the present invention, the electrolyte preferably includes one or more of lithium salts, sodium salts and potassium salts, the lithium salt more preferably includes one or more of lithium perchlorate, lithium bromide and lithium chloride, the sodium salt is more preferably sodium chloride, and the potassium salt is more preferably potassium chloride. The function of the electrolyte is to improve the ionic conductivity of the aqueous solution and promote the improvement of the optical switching performance of the system.

[0056] In the present invention, the mass ratio of the soluble metal salt to the electrolyte is preferably 6-18:50-100, specifically 6:50-100, 8:50-100, 11:50-100, 13:50-100, 15:50-100 or 18:50-100.

[0057] In the present invention, the mixing preferably further comprises adding an inorganic acid.

[0058] In the present invention, the inorganic acid is preferably a hydrochloric acid solution, the concentration of the hydrochloric acid solution is preferably 1.2 mol / L, the dosage ratio of the soluble metal salt to the hydrochloric acid solution is preferably 6-18 mg:2-10 mL, specifically 6 mg:4 mL, 8 mg:4 mL, 11 mg:4 mL, 13 mg:4 mL, 15 mg:4 mL or 18 mg:4 mL; the function of the hydrochloric acid solution is to increase the solubility of metal ions (such as bismuth ions) and prevent the hydrolysis of metal ions to produce insoluble substances (such as bismuth hydroxide).

[0059] In the present invention, the electrochromic hydrogel is preferably prepared by a method comprising the following steps:

[0060] mixing a soluble metal salt, an electrolyte and water to obtain a metal electrodeposition aqueous solution;

[0061] The metal electrodeposition aqueous solution is poured into the hydrogel to obtain the electrochromic hydrogel.

[0062] The present invention has no particular limitation on the specific type of the soluble metal salt, and raw materials familiar to those skilled in the art may be used.

[0063] In the present invention, the electrolyte preferably includes one or more of lithium salts, sodium salts and potassium salts, the lithium salt more preferably includes one or more of lithium perchlorate, lithium bromide and lithium chloride, the sodium salt is more preferably sodium chloride, and the potassium salt is more preferably potassium chloride. The function of the electrolyte is to improve the ionic conductivity of the aqueous solution and promote the improvement of the optical switching performance of the system.

[0064] In the present invention, the mass ratio of the soluble metal salt to the electrolyte is preferably 6-18:50-100, specifically 6:50-100, 8:50-100, 11:50-100, 13:50-100, 15:50-100 or 18:50-100.

[0065] In the present invention, the mixing preferably further comprises adding an inorganic acid.

[0066] In the present invention, the inorganic acid is preferably a hydrochloric acid solution, the concentration of the hydrochloric acid solution is preferably 1.2 mol / L, the dosage ratio of the soluble metal salt to the hydrochloric acid solution is preferably 6-18 mg:2-10 mL, specifically 6 mg:4 mL, 8 mg:4 mL, 11 mg:4 mL, 13 mg:4 mL, 15 mg:4 mL or 18 mg:4 mL; the function of the hydrochloric acid solution is to increase the solubility of metal ions (such as bismuth ions) and prevent the hydrolysis of metal ions to produce insoluble substances (such as bismuth hydroxide).

[0067] In the present invention, the preferred concentration of metal ions in the metal electrodeposition aqueous solution is 1 to 100 g / L, specifically 1, 6, 15, 18, 20, 50, 80 or 100 g / L.

[0068] After obtaining the metal electrodeposition aqueous solution, the present invention pours the metal electrodeposition aqueous solution into the hydrogel to obtain the electrochromic hydrogel.

[0069] In the present invention, the hydrogel preferably includes one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyethylene oxide and polyhydroxyethyl methacrylate.

[0070] In a specific embodiment of the present invention, the preparation method of the polyacrylamide is as follows:

[0071] Acrylamide monomer, initiator, cross-linking agent, catalyst and water are mixed to obtain a precursor solution, and the precursor solution is degassed and then subjected to polymerization reaction to obtain the polyacrylamide.

[0072] In the present invention, the amount of the acrylamide monomer is preferably 5% to 10% of the mass of water, the amount of the initiator is preferably 0.1% to 1.0% of the mass of water, the amount of the cross-linking agent is preferably 0.05% to 2.0% of the mass of water, and the amount of the catalyst is preferably 0.1% to 2.0% of the mass of water.

[0073] In the present invention, the initiator is preferably a photoinitiator or a thermal initiator, more preferably one or more of potassium persulfate, ammonium persulfate, cerium ammonium nitrate, Irgacure 2959 (hydrophilic photoinitiator) and Irgacure 651 (hydrophobic photoinitiator); the crosslinking agent is preferably N,N'-methylenebisacrylamide, an epoxy compound or a multifunctional monomer; the catalyst is preferably N,N,N',N'-tetramethylethylenediamine.

[0074] In the present invention, the degassing treatment is preferably carried out in a vacuum chamber, and the obtained solution is sealed and then put into an oven for baking at 60° C. for 12 hours to obtain the polyacrylamide.

[0075] In the present invention, the volume ratio of the metal electrodeposition aqueous solution to the hydrogel is preferably 1:1-5, specifically 1:1, 1:2, 1:3, 1:4 or 1:5. By controlling the volume ratio of the metal electrodeposition aqueous solution to the hydrogel, the proportion of the metal electrodeposition aqueous solution in the overall electrochromic hydrogel can be controlled, thereby regulating the electrochromic properties of the hydrogel.

[0076] In the present invention, the metal electrodeposition aqueous solution and the hydrogel are preferably placed in the same container, sealed and allowed to stand for 12 hours to obtain the electrochromic hydrogel. During the standing process, the metal electrodeposition aqueous solution is adsorbed into the skeleton network structure of the hydrogel by utilizing the swelling effect of the hydrogel.

[0077] In the present invention, the thickness of the electrolyte layer is preferably 0.01 to 1 mm, and specifically may be 0.01, 0.05, 0.1, 0.2, 0.5 or 1 mm.

[0078] The present invention also provides a method for preparing the metal electrodeposition color-changing device described in the above technical solution, comprising the following steps:

[0079] Depositing on the surface of the first substrate to obtain a first transparent conductive metal oxide layer;

[0080] Depositing on the surface of the second substrate to obtain a second transparent conductive metal oxide layer;

[0081] coating a conductive polymer dispersion on the surface of the second transparent conductive metal oxide layer to form a film to obtain a conductive polymer film;

[0082] A spacing groove is placed on the surface of the first transparent conductive metal oxide layer, and then the spacing groove is filled with electrolyte material, and then covered with the conductive polymer film to obtain the metal electrodeposition color-changing device.

[0083] The present invention has no particular limitation on the specific method of deposition, and any method familiar to those skilled in the art may be used.

[0084] After obtaining the second transparent conductive metal oxide layer, the present invention coats the surface of the second transparent conductive metal oxide layer with a conductive polymer dispersion to form a film, thereby obtaining a conductive polymer film.

[0085] In the present invention, the coating is preferably performed by blade coating, spin coating, drop coating or spray coating.

[0086] In the present invention, the spin coating rotation speed is preferably 4000 rpm, and the spin coating time is preferably 30 s.

[0087] The present invention has no particular limitation on the type of dispersant in the conductive polymer dispersion and the concentration of the dispersion, as long as the film thickness can be 500 nm to 10 μm.

[0088] After obtaining the conductive polymer film, the present invention places a spacing groove on the surface of the first transparent conductive metal oxide layer, then fills the spacing groove with electrolyte material, and then covers the conductive polymer film to obtain the metal electrodeposition color-changing device.

[0089] In the present invention, the material of the spacing groove is preferably adhesive tape, polydimethylsiloxane (PDMS), light-curable resin or thermosetting resin.

[0090] The present invention also provides the application of the metal electrodeposition color-changing device described in the above technical solution in the fields of anti-glare rearview mirrors, building curtain walls, automobile glass, electronic tags, electronic billboards, smart windows and reflective displays.

[0091] The present invention has no particular limitation on the application, and any method known to those skilled in the art may be used.

[0092] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0093] Example 1

[0094] preparation Figure 1 The metal electrodeposition color-changing device of the structure shown comprises the following steps:

[0095] 1. Preparation of Electrochromic Hydrogel

[0096] Preparation of polyacrylamide hydrogel: 1.5 g acrylamide was dissolved in 20 mL deionized water, 2 mg N, N'-methylenebisacrylamide and 3 mg ammonium persulfate were added to obtain a clear precursor solution, and then the solution was degassed in a vacuum chamber. After the above treatment was completed, 4 mg N, N, N'-, N'-tetramethylethylenediamine was added, and the solution was placed in an oven and baked at 60 ° C for 12 h.

[0097] Preparation of metal electrodeposition aqueous solution: First weigh 60 mg of anhydrous copper chloride, 50 mg of anhydrous bismuth chloride and 500 mg of lithium bromide, add 4 mL of 1.2 mol / L hydrochloric acid solution, and finally add deionized water and stir thoroughly to make a 10 mL solution.

[0098] Preparation of electrochromic hydrogel: The above-mentioned metal electrodeposition aqueous solution and hydrogel are placed in the same container at a volume ratio of 1:1, sealed and allowed to stand for 12 hours to obtain an electrochromic hydrogel based on the metal electrodeposition principle.

[0099] 2. Preparation of conductive polymer film: Select polythiophene derivative, poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate) on a glass substrate deposited with a second transparent conductive metal oxide layer of indium tin oxide, and apply a dispersion of PEDOT:PSS by spin coating (rotation speed 4000 rpm, spin coating time 30 s) on the surface of the second transparent conductive metal oxide layer to form a film with a thickness of 300 nm.

[0100] 3. Preparation of metal electrodeposition color-changing device: Deposit on the surface of the first substrate (glass substrate) to obtain the first transparent conductive metal oxide layer (indium tin oxide), place a spacing groove (made of polydimethylsiloxane) on the surface, then fill the spacing groove with electrochromic hydrogel (thickness of 200μm), and then cover it with a conductive polymer film to obtain a metal electrodeposition color-changing device.

[0101] Figure 3 Schematic diagram of the color switching state of the metal electrodeposition color-changing device of Example 1, Figure 4 is the UV-visible-near infrared transmission spectrum of the metal electrodeposition color-changing device of Example 1 at different voltages, Figure 5The cyclic stability of the metal electrodeposition color-changing device of Example 1 shows that the prepared metal electrodeposition color-changing device can achieve reversible switching between colorless and black, has a lower operating voltage of -1.2V, and has good cyclic stability. The optical change has basically no attenuation after a color change-fading cycle of more than 20,000 seconds.

[0102] Example 2

[0103] The same as Example 1, the only difference is that poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) is replaced by poly[[3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6,8-diyl]].

[0104] Figure 6 Schematic diagram of the color switching state of the metal electrodeposition color-changing device of Example 2, Figure 7 The UV-visible-near infrared transmission spectra of the metal electrodeposition color-changing device of Example 2 at different voltages show that the obtained metal electrodeposition color-changing device can achieve reversible switching between magenta and black, and also has a lower operating voltage (-1.2V). It also has good cycle stability, and the optical properties are basically not attenuated after the color change-fading cycle of 100,000 seconds ( Figure 8 ).

[0105] Example 3

[0106] The same as Example 1, except that the thickness of the conductive polymer film is 65, 150, 250 and 500 nm respectively.

[0107] Fig. 9 The color switching state diagram and optical transmittance curve of the metal electrodeposition device prepared in Example 3, where the color switching state diagram is 65, 150, 250 and 500 nm from left to right. It can be seen that the optical transmittance of PEDOT:PSS with different thicknesses is different. As the thickness increases, the color of the ITO electrode containing the PEDOT:PSS film gradually darkens and the transmittance gradually decreases. PEDOT:PSS devices with different thicknesses all have reversible optical switching properties, and as the thickness increases, the optical modulation ability gradually increases. The color change voltage of the metal electrodeposition device prepared in Example 2 is 1.2V, and the fading voltage is -0.2V. Fig.10 The effect of metal electrodeposition devices made of PEDOT:PSS of different thicknesses on the electrochromic response ability shows that with the increase of PEDOT:PSS thickness, the initial transmittance of the device gradually decreases, but the optical modulation ability (transmittance change under the same voltage) improves.

[0108] Comparative Example 1

[0109] preparation Figure 2 The metal electrodeposition device of the structure shown comprises the following steps:

[0110] The preparation of the electrochromic hydrogel is the same as that in Example 1.

[0111] Preparation of metal electrodeposition hydrogel devices:

[0112] Two transparent conductive electrodes (made of indium tin oxide) were deposited on the surfaces of two glass substrates respectively, and a spacing groove (made of polydimethylsiloxane) was placed between the two transparent conductive electrodes. Then, the spacing groove was filled with electrochromic hydrogel (thickness of 200 μm) to obtain a metal electrodeposition device.

[0113] Fig.11 This is a schematic diagram of the color switching state of the metal electrodeposition device in comparative example 1. It can be seen that the operating voltage of the device is too large and needs to be above 2V to have a significant change. The high energy consumption and stability risks caused by the high voltage are difficult to avoid. Fig.12 As shown in the cyclic stability of the metal electrodeposition device of comparative example 1, it can be seen that the optical change has been significantly attenuated after the color change-fading cycle has lasted for 20,000 seconds.

[0114] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A metal electrodeposition color-changing device, characterized in that: The invention comprises a first substrate, a first transparent conductive metal oxide layer, an electrolyte layer, a conductive polymer film, a second transparent conductive metal oxide layer and a second substrate which are stacked in sequence, wherein the electrolyte layer contains metal ions.

2. The metal electrodeposition color-changing device according to claim 1, characterized in that: The material of the conductive polymer film includes one or more of polyaniline, polythiophene, polypyrrole, polyparaphenylene, polyparaphenylene and polythiophene derivatives.

3. The metal electrodeposition color-changing device according to claim 2, characterized in that: The polythiophene derivatives include poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) and / or poly[[3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6,8-diyl]].

4. The metal electrodeposition color-changing device according to claim 1 or 2, characterized in that: The thickness of the conductive polymer film is 50nm-2μm.

5. The metal electrodeposition color-changing device according to claim 1, characterized in that: The electrolyte layer is an aqueous solution or an electrochromic hydrogel.

6. The metal electrodeposition color-changing device according to claim 1, characterized in that: The metal ions include one or more of copper ions, zinc ions, bismuth ions and silver ions.

7. The metal electrodeposition color-changing device according to claim 5, characterized in that: The electrochromic hydrogel is prepared by a method comprising the following steps: mixing a soluble metal salt, an electrolyte and water to obtain a metal electrodeposition aqueous solution; The metal electrodeposition aqueous solution is poured into the hydrogel to obtain the electrochromic hydrogel.

8. The metal electrodeposition color-changing device according to claim 7, characterized in that: The hydrogel includes one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyethylene oxide and polyhydroxyethyl methacrylate.

9. The method for preparing a metal electrodeposition color-changing device according to any one of claims 1 to 8, characterized in that: The following steps are involved: Depositing on the surface of the first substrate to obtain a first transparent conductive metal oxide layer; Depositing on the surface of the second substrate to obtain a second transparent conductive metal oxide layer; coating a conductive polymer dispersion on the surface of the second transparent conductive metal oxide layer to form a film to obtain a conductive polymer film; A spacing groove is placed on the surface of the first transparent conductive metal oxide layer, and then the spacing groove is filled with electrolyte material, and then covered with the conductive polymer film to obtain the metal electrodeposition color-changing device.

10. Application of the metal electrodeposition color-changing device according to any one of claims 1 to 8 or the metal electrodeposition color-changing device prepared by the preparation method according to claim 9 in the fields of anti-glare rearview mirrors, building curtain walls, automobile glass, electronic tags, electronic billboards, smart windows and reflective displays.

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