Reflective integrated electrochromic device and preparation method therefor

Abstract

A reflective integrated electrochromic device, sequentially comprising: a first substrate layer (11), a working electrode layer (12), an integrated electrochromic layer (13), a counter electrode layer (14), and a second substrate layer (15), wherein the integrated electrochromic layer (13) comprises a metal source compound, the metal source compound being selected from one or more of silver chloride, silver acetate, silver nitrate, silver perchlorate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver triflate, silver bistrifluoromethanesulfonimide, copper fluoride, copper chloride, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, gold monochloride, aurous sulfide, nickel chloride, nickel sulfate, cobalt chloride, and platinum chloride. The dynamic change range of the transmittance / reflectance of the device is relatively large, and the device can achieve simultaneous management of light and heat, and can maintain a stable colored or faded state for one month, or even several months, under no-load conditions.

Description

A reflective integrated electrochromic device and its fabrication method

[0001] This application claims priority to the following Chinese patent applications filed on June 21, 2024, with application number 202410813309.6, entitled "A Reflective Integrated Electrochromic Device and its Preparation Method"; filed on September 6, 2024, with application number 202411257413.8, entitled "An Integrated Electroreflective Device and its Preparation Method"; filed on September 6, 2024, with application number 202411253687X, entitled "Slurry, Reversible Metal Electrodeposition Device and its Preparation Method"; and filed on September 6, 2024, with application number 202411253689.9, entitled "A Solvent-Free Acrylic Ester System Electroreflective Device and its Preparation Method", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to the field of electrochromic technology, and more particularly to a reflective integrated electrochromic device and its fabrication method. Background Technology

[0003] Electrochromic devices generally refer to optoelectronic devices that change color by applying a certain voltage. Currently, they mainly work by altering the valence state or molecular structure of compounds through redox reactions at the anode or cathode, thereby changing their absorption wavelength. Absorption-type electrochromic devices are already available on the market, while reflection-type electrochromic devices are still in the research stage.

[0004] Reversible metal electrodeposition devices (RMEDs) are a new type of electrochromic device that has excellent spectral modulation capabilities in the visible and infrared bands. They also have unique advantages such as simple structure, low power consumption, and multi-color state modulation, showing great application potential in fields such as smart windows, thermal management, and information display.

[0005] The most critical factor currently hindering the development of reversible metal electrodeposition devices is the short steady-state time, typically ranging from a few seconds to several hours, requiring continuous voltage application to maintain the colored or uncolored state. The best reported open-circuit stability to date does not exceed 2 hours. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a reflective integrated electrochromic device and its preparation method, which can maintain a stable coloring or fading state for one month or even several months under no-load conditions.

[0007] To achieve the above objectives, the present invention provides a reflective integrated electrochromic device, comprising, in sequence:

[0008] First substrate layer, working electrode layer, integrated electrochromic layer, counter electrode layer, second substrate layer;

[0009] The integrated electrochromic layer includes a metal source compound;

[0010] The metal source compound is selected from one or more of the following: silver chloride, silver acetate, silver nitrate, silver perchlorate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, silver bis(trifluoromethanesulfonyl)imide, copper fluoride, copper chloride, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, gold chloride, gold sulfide, nickel chloride, nickel sulfate, cobalt chloride, and platinum chloride.

[0011] Preferably, the metal source compound is selected from one or more of silver chloride, silver hexafluorophosphate, silver tetrafluoroborate, or silver bis(trifluoromethanesulfonyl)imide.

[0012] More preferably, the metal source compound is selected from silver chloride.

[0013] The mass fraction of the metal source compound in the integrated electrochromic layer is preferably 1% to 30%.

[0014] The present invention uses the above-mentioned metal source compound, which does not produce Ag during the internal redox reaction when a low voltage (0.1-1.5V) is applied to the device. + Other redox electron pairs besides Ag, consisting only of Ag + The charge transfer of Ag enables the deposition and dissolution of Ag, thereby achieving the coloring and fading of the device, which greatly extends the steady-state time of the device. Under no-load conditions, it can maintain a stable colored or faded state for one month or even several months.

[0015] In this invention, the integrated electrochromic layer further includes an ionic liquid.

[0016] The aforementioned ionic liquid is preferably one or more of alkyl imidazole salts, alkyl pyridine salts, alkyl pyrrole salts, alkyl quaternary ammonium salts, alkyl quaternary phosphine salts, fluoroalkyl imidazole salts, fluoroalkyl pyridine salts, fluoroalkyl pyrrole salts, fluoroalkyl quaternary ammonium salts, and fluoroalkyl quaternary phosphine salts, and more preferably alkyl imidazole salts.

[0017] The mass fraction of the aforementioned ionic liquid in the integrated electrochromic layer is preferably 20% to 90%.

[0018] The function of the aforementioned ionic liquid is to provide the mass transfer conditions for silver ions and enhance ion mobility.

[0019] In some specific embodiments of the present invention, the integrated electrochromic layer further includes one or more of a polymer compound, a solvent, and an additive.

[0020] The aforementioned polymeric compounds preferably include one or more of polyacrylic acid and its derivatives, polyacrylate and its derivatives, hydroxyethyl polyacrylate and its derivatives, polyvinylpyrrolidone and its derivatives, polyurethane and its derivatives, polyepoxy resin and its derivatives, and copolymers of the aforementioned polymers.

[0021] In this invention, the aforementioned polymer compound is generated through integrated polymerization during the device fabrication process.

[0022] Preferably, the aforementioned polymer compound is generated by an integrated polymerization reaction within the device using one or more of the following polymeric monomers, initiators, crosslinking agents, catalysts, and polymerization inhibitors.

[0023] Preferably, the polymerizing monomer includes one or more of the following: acrylic acid and its derivatives, acrylates and their derivatives, hydroxyethyl acrylate and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, diphenylmethane diisocyanate and its derivatives, toluene diisocyanate and its derivatives, isophorone diisocyanate and its derivatives, dicyclohexylmethane diisocyanate and its derivatives, hexamethylene diisocyanate and its derivatives, L-lysine diisocyanate and its derivatives, polyols and their derivatives, polyamines and their derivatives, phenyl dioxide epoxy resin and its derivatives, glycidyl ether and its derivatives.

[0024] The initiator preferably includes one or more of the following: diazonium salts and their derivatives, diaryliodomonium salts and their derivatives, triarylthiomonium salts and their derivatives, alkylthiomonium salts and their derivatives, iron aromatic salts and their derivatives, sulfonyloxyketones and their derivatives, triarylsiloxanes and their derivatives, benzoin and its derivatives, benzoyl and its derivatives, alkylphenyl ketones and their derivatives, acylphosphoxides and their derivatives, benzophenones and their derivatives, 2-hydroxy-2-methylphenylacetone and its derivatives, thioxanthones and their derivatives, and lithium phenyl(2,4,6-trimethylbenzoyl)phosphate and its derivatives.

[0025] The crosslinking agent preferably includes one or more of the following: ethylene glycol dimethacrylate and its derivatives, polyethylene glycol dimethacrylate and its derivatives, polydipentaerythritol pentaacrylate and its derivatives, ethoxylated trimethylolpropane triacrylate and its derivatives, N,N'-methylenebisacrylamide and its derivatives.

[0026] The catalyst preferably includes one or more of the following: dibutyltin dilaurate and its derivatives, di(dodecylthio)dibutyltin and its derivatives, dibutyltin diacetate and its derivatives, stannous octoate and its derivatives.

[0027] The polymerization inhibitor preferably includes one or more of the following: hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dibutylbiphenyl, bisphenol A, tetrachlorobenzoquinone, 1,4-naphthoquinone, aromatic nitro compounds, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, sodium sulfate, sodium sulfide, ammonium thiocyanate, and sodium dithiocarbamate.

[0028] More preferably, it is acrylic acid and its derivatives, lithium phenyl (2,4,6-trimethylbenzoyl)phosphate and its derivatives, polyethylene glycol dimethacrylate and its derivatives.

[0029] The mass fraction of the aforementioned polymer compound in the integrated electrochromic layer is preferably 5% to 50%.

[0030] The aforementioned polymer compounds serve to support the mechanical structure of the entire electrochromic layer, ensure compatibility with active substances and ionic liquids to prevent precipitation, and provide a favorable environment for ion migration.

[0031] Preferably, the solvent comprises one or more of γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methylpyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, sulfolane and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives; more preferably, propylene carbonate and its derivatives and / or dimethyl sulfoxide and its derivatives.

[0032] When the integrated electrochromic layer of the present invention is a solid system, no solvent needs to be added to the system.

[0033] The aforementioned additives preferably include, but are not limited to, coupling agents, antioxidants, light stabilizers, thickeners, electrolyte supplements, and spacers.

[0034] The present invention does not impose any particular limitation on the types of coupling agents, antioxidants, light stabilizers, thickeners, electrolyte supplements, and spacers mentioned above, and can be any applicable types known to those skilled in the art.

[0035] Preferably, the additive includes one or more of the following: silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents (including but not limited to aluminum-zirconate, aluminum-titanium composite coupling agents, etc.), rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers (HALS), hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, and silica microspheres; more preferably, silane coupling agents, acrylate polyols, lithium nitrate, and polyacrylate microspheres.

[0036] The mass fraction of the above-mentioned additives in the integrated electrochromic layer is preferably 0-5%.

[0037] The additives mentioned above enhance the interfacial bonding between the electrochromic layer and the electrode layer, increase the electrochromic layer's tolerance to external oxygen and ambient light, and enhance conductivity and structural support.

[0038] This invention employs in-situ polymerization of monomers to prepare the integrated electrochromic layer. A slurry or solution containing the raw materials for the integrated electrochromic layer is first prepared, and then cured in situ within the device to form a gel-like or solid integrated electrochromic layer. Therefore, no solvent is required, avoiding problems such as bubbling, wrinkling, cracking of the active layer, and performance degradation caused by solvent evaporation during later use.

[0039] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver chloride, 1-butyl-3-methylimidazolium chloride, hydroxyethyl acrylate, ethylene glycol diacrylate, lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, and vinylsiloxane.

[0040] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver chloride, 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, acrylic acid, N,N'-methylenebisacrylamide, 2-hydroxy-2-methylphenylacetone, hydroquinone, and γ-glycidoxypropyltrimethoxysilane.

[0041] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver bis(trifluoromethanesulfonyl)imide, N-butylpyridine hexafluorophosphate, ethylene glycol monoethyl ether, aminosiloxane, acrylate polyol, isophorone diisocyanate, dibutyltin diacetate, and lithium nitrate.

[0042] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes copper chloride, 1-butyl-3-methylimidazolium chloride, polyethylene glycol 1000, and lithium nitrate.

[0043] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes nickel chloride, silver chloride, 1-butyl-3-methylimidazolium chloride, acrylic acid, ethylene glycol dimethacrylate, lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, and vinylsiloxane.

[0044] In some specific embodiments of the present invention, the reflective integrated electrochromic device provided by the present invention includes an integrated electrochromic layer; the integrated electrochromic layer includes an ionic liquid.

[0045] The ionic liquid includes a long-chain alkyl compound having six or more carbon atoms.

[0046] The integrated electrochromic layer can also be called an integrated electroreflective layer.

[0047] This invention improves the water and oxygen resistance of the integrated electrochromic layer by increasing the carbon chain length of the ionic liquid molecular structure, thereby improving the device's reflection performance and cycle stability, reducing the device's packaging difficulty, and making it easier to industrialize.

[0048] Preferably, the long-chain alkyl compound has 6 to 20 carbon atoms. In some specific embodiments of the present invention, the long-chain alkyl compound has 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, or any of the above values ​​as the upper or lower limit.

[0049] Preferably, the long-chain alkyl compound is selected from one or more of alkyl imidazolium salts, alkyl pyridine salts, alkyl pyrrole salts, alkyl quaternary ammonium salts, alkyl quaternary phosphine salts, fluoroalkyl imidazolium salts, fluoroalkyl pyridine salts, fluoroalkyl pyrrole salts, fluoroalkyl quaternary ammonium salts, and fluoroalkyl quaternary phosphine salts.

[0050] In some specific embodiments of the present invention, the long-chain alkyl compound is selected from one or more of 1-C6 to C20 alkyl-3-methylimidazolium salts, 1-vinyl-3-C6 to C20 alkylimidazolium salts, and N-C6 to C20 alkylpyridinium salts.

[0051] The anions of the aforementioned long-chain alkyl compounds include, but are not limited to, halide ions, tetrafluoroborate ions, hexafluorophosphate ions, fluorosulfonyl imide ions, trifluoromethanesulfonyl imide ions, and bis(trifluoromethanesulfonyl imide) ions.

[0052] In some specific embodiments of the present invention, the long-chain alkyl compound is selected from one or more of 1-dodecyl-3-methylimidazolium chloride, 1-vinyl-3-hexylimidazolium trifluoromethanesulfonylimide salt, 1-vinyl-3-dodecylimidazolium trifluoromethanesulfonylimide salt, N-dodecylpyridine hexafluorophosphate, N-eicosylpyridine hexafluorophosphate, and 1-dodecyl-3-methylimidazolium trifluoromethanesulfonylimide salt.

[0053] The mass content of the ionic liquid in the integrated electrochromic layer is preferably 20% to 90%.

[0054] The present invention does not specifically limit the other components of the integrated electrochromic layer, and can be any electrochromic layer known to those skilled in the art that is suitable for reflective integrated electrochromic devices.

[0055] Preferably, the integrated electrochromic layer further includes a metal source, and one or more of a polymer compound, solvent, and additives.

[0056] The metal source is an essential component, preferably one or more of the following metal compounds: silver chloride, silver bromide, silver iodide, silver acetate, silver nitrate, silver perchlorate, silver perbromate, silver periodate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, silver bis(trifluoromethanesulfonyl)imide, copper fluoride, copper chloride, copper bromide, copper iodide, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, gold chloride, gold sulfide, nickel chloride, nickel sulfate, cobalt chloride, platinum chloride, etc. In some specific embodiments of the present invention, the metal source is silver nitrate, silver bromide, silver bis(trifluoromethanesulfonyl)imide, or copper chloride.

[0057] The mass content of the metal source in the integrated electrochromic layer is preferably 1% to 30%.

[0058] In some specific embodiments of the present invention, the integrated electrochromic layer further includes one or more of polymer compounds, solvents, and additives. The above components are not essential components and can be freely selected according to different types of devices.

[0059] The selection of the aforementioned polymer compounds, solvents, and additives, as well as their mass content in the integrated electrochromic layer, are the same as described above and will not be repeated here.

[0060] In this invention, the aforementioned polymeric compound can be generated by integrated polymerization during the device fabrication process. Optionally, the aforementioned polymeric compound can be generated by integrated polymerization reaction of one or more of polymeric monomers, initiators, crosslinking agents, catalysts, and polymerization inhibitors inside the device.

[0061] The selection of the above-mentioned monomers, initiators, crosslinking agents, catalysts, and polymerization inhibitors is the same as described above and will not be repeated here.

[0062] The mass content of the aforementioned polymeric compound in the integrated electrochromic layer is preferably 5% to 50%.

[0063] The solvent content in the integrated electrochromic layer is preferably 0% to 20% by mass.

[0064] The role of the solvent mentioned above is to dissolve the components so that they do not precipitate, while providing a good environment for ion migration.

[0065] In preparing the integrated electrochromic layer, the present invention uses in-situ polymerization of monomers. The specific polymerization method is the same as described above and will not be repeated here.

[0066] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver nitrate, 1-dodecyl-3-methylimidazolium chloride, hydroxyethyl acrylate, ethylene glycol diacrylate, lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, propylene carbonate, vinylsiloxane, and polyglycerol.

[0067] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver bromide, 1-vinyl-3-dodecylimidazolium trifluoromethanesulfonylimide salt, acrylic acid, N,N'-methylenebisacrylamide, 2-hydroxy-2-methylphenylacetone, hydroquinone, and γ-glycidoxypropyltrimethoxysilane.

[0068] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes silver bis(trifluoromethanesulfonyl)imide, N-dodecylpyridine hexafluorophosphate, ethylene glycol monoethyl ether, aminosiloxane, acrylate polyol, isophorone diisocyanate, dibutyltin diacetate, and lithium nitrate.

[0069] In some specific embodiments of the present invention, the slurry forming the integrated electrochromic layer includes copper chloride, 1-dodecyl-3-methylimidazolium chloride, polyethylene glycol 1000, and lithium nitrate.

[0070] This invention utilizes long-chain alkyl compounds as ionic liquids to prepare electrochromic devices, improving the devices' resistance to water and oxygen. The longer alkyl chains adjust the electrolyte viscosity, facilitating the formation of smaller, denser, and more uniformly distributed electrodeposited metal nanoparticles. This results in faster switching speeds, excellent cycle durability, and small-particle-size, uniform electrodeposited nanoparticle films. Even with simple packaging, good electrodeposition effects and superior cycle stability can be achieved, which also allows for precise control of device performance through circuitry.

[0071] Figure 1 is a schematic diagram of the structure of the reflective integrated electrochromic device provided by the present invention. In the figure, 11 is the first substrate layer, 12 is the working electrode layer, 13 is the integrated electrochromic layer, 14 is the counter electrode layer, and 15 is the second substrate layer.

[0072] When electroplated metal cations undergo a reduction reaction on the working electrode layer 12 to form a metal thin film, the metal plate, metal mesh, or foil on the counter electrode layer 14 undergoes an oxidation reaction, turning into metal cations that are released into the integrated electrochromic layer 13. When the voltage polarity is reversed, the metal thin film formed on the working electrode layer 12 is oxidized back into metal cations, leaving the working electrode layer 12 and redissolving into the integrated electrochromic layer 13. The counter electrode layer 14 also undergoes a corresponding reduction reaction. At this point, the electrochromic device completes its transition to a non-reflective state.

[0073] In this invention, there is no special limitation on the thickness of the working electrode layer and the counter electrode layer, and they can be conventional thicknesses known to those skilled in the art.

[0074] In some specific embodiments of the present invention, the thickness of the working electrode layer is 1 to 20 nm, more preferably 3 to 10 nm.

[0075] Preferably, the thickness of the working electrode layer is 5–20 nm, more preferably 8–10 nm. Preferably, when the counter electrode layer is a mesh counter electrode layer, the thickness is 1–15 μm, more preferably 8–10 μm, and the porosity is 20%–90%, more preferably 60%–70%. When the counter electrode layer is a film counter electrode layer, the thickness is 1–20 nm, more preferably 3–10 nm.

[0076] In some specific embodiments of the present invention, the thickness of the film-electrode layer is 5-20 nm, more preferably 8-10 nm.

[0077] The thickness of the integrated electrochromic layer is preferably 5–3000 μm, more preferably 20–500 μm. In some specific embodiments of the present invention, the thickness of the integrated electrochromic layer 13 is 50 μm, 100 μm, or 200 μm.

[0078] In this invention, the conductive layer material of the counter electrode is selected from a transparent conductive metal electrode.

[0079] Preferably, the transparent conductive metal electrode is selected from one or more of the following: a mesh or film made of copper nanowires, silver nanowires, aluminum nanowires, copper mesh, silver mesh, aluminum mesh, indium tin oxide-copper multilayer composite film or mesh, indium tin oxide-silver multilayer composite film or mesh, indium tin oxide-aluminum multilayer composite film or mesh, and silver nanoparticle paste.

[0080] This invention uses a transparent conductive metal electrode as the counter electrode, which can play a role in electron transport and participate in redox while ensuring the transparency of the device. Based on this, this invention has for the first time prepared a reflective integrated transparent electrochromic device.

[0081] Preferably, the conductive layer material of the working electrode is selected from one or more of the following: indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, metallic copper, metallic silver, metallic aluminum, metallic gold, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, indium tin oxide-gold multilayer composite material, graphene, and carbon nanotubes to make a mesh-like or planar transparent conductive film. More preferably, it is a mesh-like or planar transparent conductive film made of metallic copper, metallic silver, metallic gold, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, or indium tin oxide-gold multilayer composite material.

[0082] In some specific embodiments of the present invention, the conductive layer material of the working electrode layer is selected from one or more of the following materials: indium tin oxide (ITO), zinc aluminum oxide (AZO), fluorine-doped tin oxide (FTO), copper nanowires, silver nanowires, aluminum nanowires, copper mesh, silver mesh, aluminum mesh, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, graphene, carbon nanotubes, and silver nanopaste.

[0083] The present invention does not specifically limit the preparation methods of the above-mentioned counter electrode and working electrode, which can be commercially available electrodes or electrodes prepared according to methods well known to those skilled in the art. These methods include, but are not limited to, forming conductive films or conductive plates on the surface of flexible or rigid substrates by means of magnetron sputtering, screen printing, ion beam evaporation, or chemical deposition.

[0084] The present invention does not have any particular limitation on the material of the first substrate layer and the second substrate layer, and can be any substrate material known to those skilled in the art. Preferably, it is an inorganic substrate, an organic substrate, or an inorganic-organic composite substrate.

[0085] The inorganic substrate material is preferably glass, diamond, ceramic, or similar materials. Its thickness is preferably 500–50000 μm.

[0086] The organic substrate material is preferably one or more of the following: polymethyl methacrylate and its derivatives, polyethylene terephthalate and its derivatives, polyethylene terephthalate and its derivatives, cyclic olefin copolymers and their derivatives, cellulose triacetate and its derivatives, polyethersulfone resins and their derivatives, polyimide and its derivatives, polycarbonate and its derivatives, polyethylene, polypropylene, polyvinyl chloride, thermoplastic polyurethane, polysulfone, and acrylonitrile-butadiene-styrene terpolymers. Its thickness is preferably 20–50,000 μm.

[0087] In this invention, at least one side of the first substrate layer and the second substrate layer is a transparent material, and the other side can be a transparent or non-transparent material.

[0088] In some specific embodiments of the present invention, the reflective integrated electrochromic device provided by the present invention is a solvent-free acrylate system electrochromic device, including an electrochromic layer; the electrochromic layer is formed by curing an electrochromic slurry; the electrochromic slurry includes a metallic silver compound component, a polymerizable monomer, and additives.

[0089] The polymerizable monomers include hydrophobic polymeric monomers such as acrylates.

[0090] Preferably, the additive comprises an ionic liquid; the molecular structure of the ionic liquid contains hydrophobic long alkyl and / or aryl functional groups.

[0091] In this invention, the thickness range of the electrochromic layer is preferably 10μm to 300μm, more preferably 50μm to 200μm, even more preferably 50μm to 150μm, and most preferably 100μm.

[0092] According to the present invention, the mass of the silver compound component is preferably 1% to 30% of the mass of the electrochromic paste, more preferably 1% to 25%, even more preferably 1% to 20%, even more preferably 1% to 15%, even more preferably 2% to 12%, even more preferably 2% to 10%, even more preferably 3% to 8%, and most preferably 4% to 5%. The silver compound component can be any silver compound well known to those skilled in the art, and there are no special limitations. In the present invention, silver chloride, silver acetate, silver nitrate, silver perchlorate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, and silver bis(trifluoromethanesulfonyl)imide are preferred.

[0093] According to the present invention, the mass of the polymerizable monomer is preferably 5% to 50% of the mass of the electrochromic paste, more preferably 8% to 50%, even more preferably 10% to 50%, even more preferably 15% to 50%, even more preferably 20% to 50%, even more preferably 25% to 50%, even more preferably 30% to 50%, even more preferably 35% to 50%, even more preferably 40% to 50%, and most preferably 44% to 50%.

[0094] In a specific embodiment of the present invention, the polymerizable monomer comprises hydrophobic acrylate polymeric monomers; the mass of the hydrophobic acrylate polymeric monomers is preferably 5% to 50% of the mass of the electrochromic slurry, more preferably 8% to 50%, even more preferably 10% to 50%, even more preferably 15% to 50%, even more preferably 20% to 50%, even more preferably 25% to 50%, even more preferably 30% to 50%, even more preferably 35% to 50%, even more preferably 40% to 50%, even more preferably 42% to 48%, even more preferably 44% to 46%, and most preferably 44% to 45%; the hydrophobic acrylate polymeric monomers preferably include methyl acrylate and its derivatives, methyl methacrylate and its derivatives, ethyl acrylate and its derivatives, ethyl methacrylate and its derivatives, propyl acrylate and its derivatives, propyl methacrylate and its derivatives, butyl acrylate and its derivatives, methyl... The invention comprises one or more of the following: butyl acrylate and its derivatives, n-pentyl acrylate and its derivatives, isoamyl acrylate and its derivatives, hexyl acrylate and its derivatives, hexyl methacrylate and its derivatives, n-octyl acrylate and its derivatives, n-octyl methacrylate and its derivatives, isooctyl acrylate and its derivatives, isooctyl methacrylate and its derivatives, lauryl acrylate and its derivatives, lauryl methacrylate and its derivatives, cyclohexyl methacrylate and its derivatives, myristyl acrylate and its derivatives, myristyl methacrylate and its derivatives, isobornyl acrylate and its derivatives, isobornyl methacrylate and its derivatives, styrene and its derivatives, dicyclopentenyl acrylate and its derivatives, benzyl acrylate and its derivatives, and benzyl methacrylate and its derivatives; in the embodiments provided by the present invention, one or more of butyl acrylate, lauryl acrylate, and myristyl acrylate are specifically used as examples.

[0095] In another specific embodiment of the present invention, the polymerizable monomer further includes a comonomer; the mass of the comonomer is preferably 1% to 30% of the mass of the electrochromic paste, more preferably 1% to 25%, even more preferably 1% to 20%, even more preferably 1% to 15%, even more preferably 2% to 12%, even more preferably 2% to 10%, even more preferably 3% to 8%, and most preferably 4% to 5%; the comonomer preferably includes one or more of acrylic monomers, acrylamide monomers, acrylate monomers, and olefin derivatives, more preferably including acrylic acid, butenedioic acid, cinnamic acid, methyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate. 4-Hydroxybutyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, glycidyl methacrylate, vinyl acetate, N-vinyl-2-imidazolium and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, acrylamide, 2-acryloylamino-2-methylpropanesulfonic acid, 2-acryloylamino-dodecyl sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, m-phenoxybenzyl acrylate, 2-phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, propoxyl nonylphenol acrylate, and dicyclopentyl methacrylate are among one or more of these.

[0096] In a specific embodiment of the present invention, the polymerizable monomer preferably further includes a crosslinking agent; the crosslinking agent can be any crosslinking agent well known to those skilled in the art, and there are no special limitations. In the present invention, it preferably includes one or more of the following: tricyclodecanediethanol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol dimethacrylate, bisphenol A diacrylate ethoxylate, tricyclodecanediethanol dimethacrylate, 1,12-dodecyl dimethacrylate, N,N-methylenebisacrylamide, and 2-hydroxyethyl methacrylate phosphate; the mass of the crosslinking agent is preferably 1% to 10% of the mass of the electrochromic slurry, more preferably 2% to 8%, even more preferably 3% to 6%, even more preferably 4% to 5%, and most preferably 4.5%; in the present invention, if the acrylate hydrophobic polymer monomer and / or comonomer in the polymerizable monomer contains multiple polymerizable functional groups, then it is not necessary to add a crosslinking agent.

[0097] According to the present invention, the mass of the additive is preferably 20% to 90% of the mass of the electrochromic paste, more preferably 25% to 85%, even more preferably 30% to 80%, even more preferably 30% to 70%, even more preferably 30% to 65%, even more preferably 40% to 60%, even more preferably 45% to 55%, and most preferably 50% to 51%.

[0098] According to the present invention, the additive preferably comprises an ionic liquid; the molecular structure of the ionic liquid comprises hydrophobic long alkyl and / or aryl functional groups.

[0099] In a specific embodiment of the present invention, the additive comprises an ionic liquid; the mass of the ionic liquid is preferably 20% to 90% of the mass of the electrochromic paste, more preferably 25% to 85%, even more preferably 30% to 80%, even more preferably 30% to 70%, even more preferably 30% to 65%, even more preferably 40% to 60%, even more preferably 40% to 50%, even more preferably 42% to 48%, even more preferably 44% to 46%, and most preferably 44% to 45%; the molecular structure of the ionic liquid comprises hydrophobic long alkyl and / or aryl functional groups; the number of carbon atoms of the hydrophobic long alkyl group is preferably... The ionic liquid is selected to be greater than or equal to 8, more preferably 8-20, even more preferably 10-18, and even more preferably 12-16; more specifically, the ionic liquid includes one or more of imidazole salt ionic liquids, pyridine salt ionic liquids, pyrrole salt ionic liquids, quaternary ammonium salt ionic liquids, quaternary phosphine salt ionic liquids, fluoroimidazolium salt ionic liquids, fluoropyridine salt ionic liquids, fluoropyrrole salt ionic liquids, fluoroquaternary ammonium salt ionic liquids, and fluoroquaternary phosphine salt ionic liquids; even more specifically, the ionic liquid is 1-octyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl... 1-3-Methylimidazolium chloride, 1-hexadecimal-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium tetrafluoroborate, 1-dodecyl-3-methylimidazolium hexafluorophosphate, 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-tetradecyl-3-methylimidazolium tetrafluoroborate, 1-tetradecyl-3-methylimidazolium hexafluorophosphate ... tetrafluorophosphate, 1-tetradecyl-3-methylimidazolium tetrafluorophosphate One or more of the following salts are used: 1-hexadecyl-3-methylimidazolium tetrafluoroborate, 1-hexadecyl-3-methylimidazolium hexafluorophosphate, 1-hexadecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidazolium salt, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium hexafluorophosphate, and 1-benzyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidazolium salt; in the embodiments provided by the present invention, 1-octyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium chloride and / or 1-benzyl-3-methylimidazolium chloride are specifically used as examples.

[0100] In another specific embodiment of the present invention, the additive further includes one or more of an initiator, a coupling agent, a surfactant, a thickener, and a spacer; the total mass of one or more of the initiator, crosslinking agent, coupling agent, surfactant, thickener, and spacer is preferably 1% to 30% of the electrochromic slurry mass, more preferably 1% to 25%, even more preferably 1% to 20%, even more preferably 1% to 15%, even more preferably 2% to 12%, even more preferably 2% to 10%, even more preferably 3% to 8%, and most preferably 4% to 6%; the initiator can be any initiator well known to those skilled in the art. There are no particular limitations, but the present invention preferably includes potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, benzaldehyde-formaldehyde trimer, acryloylcarboxylate diester, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, lithium phenyl(2,4,6-trimethylbenzoyl)phosphate, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 1-hydroxyphenylcyclohexanone, 1-hydroxy-cyclohexyl-phenyl methyl ketone, 2-hydroxy-2-methyl-1-propanone, etc. One or more of phenyl-1-propanone, benzoin dimethyl ether, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropanone; the coupling agent is any coupling agent well known to those skilled in the art and is not particularly limited, but preferably includes silane coupling agents and / or phthalate coupling agents; the surfactant is preferably any surfactant well known to those skilled in the art and is not particularly limited, but preferably includes one or more of sulfated oil, higher fatty alcohol sulfates, aliphatic sulfonates, alkyl aryl sulfonates, alkyl naphthalene sulfonates, and alkylphenol polyoxyethylene ethers; the thickener is preferably one of those in the art. Thickeners familiar to those skilled in the art are acceptable and are not particularly limited. In this invention, thickeners preferably include one or more of acrylate polyols, sodium polyacrylate, sodium polypentaerythritol acrylate, sodium alginate, and carboxymethyl cellulose. The spacers are preferably spacers familiar to those skilled in the art and are not particularly limited. In this invention, spacers preferably include one or more of polystyrene microspheres, polyacrylate microspheres, and silica microspheres. The particle size of the spacers is preferably 10–1000 μm, more preferably 50–500 μm, even more preferably 50–200 μm, even more preferably 80–150 μm, and most preferably 100 μm.

[0101] According to the present invention, the solvent-free acrylate electrochromic device preferably comprises a first substrate layer, a working electrode layer, an electrochromic layer, a counter electrode layer, and a second substrate layer arranged sequentially. Referring to Figure 1, which is a schematic diagram of the structure of the solvent-free acrylate electrochromic device provided by the present invention, 11 is the first substrate layer, 12 is the working electrode layer, 13 is the electrochromic layer, 14 is the counter electrode layer, and 15 is the second substrate layer. Specifically, the first substrate layer and the second substrate layer are each independently an inorganic substrate layer, an organic substrate layer, or an inorganic-organic composite substrate layer; and at least one of the first substrate layer and the second substrate layer is a transparent substrate layer, while the other can be a transparent substrate layer or a non-transparent substrate layer.

[0102] More specifically, the inorganic substrate layer preferably includes one or more of glass, diamond, and ceramic; the thickness of the inorganic substrate layer is preferably 500–50000 μm; the organic substrate layer preferably includes one or more of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene terephthalate, perfluoroethylene propylene, ethylene-vinyl acetate copolymer, polyimide, thermoplastic polyurethane, polysulfone, and acrylonitrile-butadiene-styrene terpolymer; the thickness of the organic substrate layer is preferably 20–5000 μm.

[0103] Specifically, the working electrode layer is a mesh-like or planar transparent conductive layer made of one or more of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, metallic copper, metallic silver, metallic aluminum, metallic gold, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, indium tin oxide-gold multilayer composite material, graphene, and carbon nanotubes. More preferably, it is a mesh-like or planar transparent conductive layer made of metallic copper, metallic silver, metallic gold, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, or indium tin oxide-gold multilayer composite material. More specifically, the working electrode layer is preferably a planar transparent conductive film. The working electrode layer is preferably formed on the surface of the first substrate layer by means of magnetron sputtering, ion beam evaporation, or chemical deposition to form a conductive film.

[0104] Specifically, the counter electrode layer is a mesh-like or planar transparent conductive layer made of one or more of the following materials: copper nanowires, silver nanowires, aluminum nanowires, metallic copper, metallic silver, metallic aluminum, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, and silver nanoparticle paste; more specifically, the counter electrode layer is preferably a mesh-like transparent conductive film; the counter electrode layer is preferably formed into a conductive film on the surface of the second substrate layer by means of screen printing, offset printing, letterpress printing, gravure printing, or laser etching.

[0105] This invention employs a solvent-free acrylate system, utilizing the compatibility between ionic liquids containing hydrophobic long alkyl and / or aryl functional groups and acrylate monomers. By using acrylate molecules with hydrophobic groups as the main polymer backbone, the integrated electrochromic layer is made into a hydrophobic layer, effectively improving the overall water and oxygen resistance and significantly enhancing the cycle stability and lifespan of the device.

[0106] In some specific embodiments of the present invention, the integrated electrochromic layer of the reflective integrated electrochromic device provided by the present invention is generated by an integrated polymerization reaction of slurry inside the device.

[0107] The slurry comprises: a metal source, a polymerizable monomer, and an initiator;

[0108] The polymerizable monomers include polymerizable monomers having ionic liquid groups and / or polymerizable monomers that can coordinate with metal ions.

[0109] Preferably, the polymerizable monomer structure having ionic liquid groups includes: polymerizable groups, organic cations, and inorganic or organic anions.

[0110] The polymerizable group can be used to carry out polymerization reactions, and preferably includes one or more of olefinic, alkyneic and epoxy groups, more preferably C2 alkenic, C3 alkenic, C4 alkenic or C5 alkenic, and even more preferably one or more of vinyl, propenic, allyl and the like.

[0111] The organic cation preferably includes one or more of the following: quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazole salt ions, pyrrole salt ions, pyridinium salt ions, piperidine salt ions, morpholine salt ions, thiophene salt ions, carbazole salt ions, and guanidine salts; preferably, the organic cation may have 1 to 2 substituents, wherein the substituents are independently C1 to C10 alkyl groups, more preferably C1 to C6 alkyl groups, and even more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or n-hexyl. In some specific embodiments of the present invention, the organic cation is methylimidazolium, ethylimidazolium, propylimidazolium, butylimidazolium, benzylimidazolium, allylimidazolium, or methylpyrrolidine, etc.

[0112] The inorganic or organic anion preferably includes one or more of the following anions:

[0113] Halogen ions, alkali salt ions, fluorine-containing anions, oxyacid anions, amino acid anions, ester anions, cyanide-containing anions, and halide metal salt anions.

[0114] Preferably, the halide ion is selected from halide ions well known in the art, such as chloride ion, bromide ion, iodide ion or bromide triantium ion.

[0115] Preferably, the alkaline salt ion is selected from alkaline salt ions well known in the art, such as hydroxide ions, carbonate ions, bicarbonate ions, bisulfate ions, phosphate ions, or hydrogen phosphate ions.

[0116] Preferably, the fluorine-containing anion is selected from fluorine-containing anions well known in the art, such as tetrafluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate ion, trifluoromethanesulfonylimide ion, antimony hexafluoride ion, or trifluoroacetate ion.

[0117] Preferably, the anion of the oxyacid is selected from anions of oxyacids well known in the art, such as sulfate ion, nitrate ion, perchlorate ion, acetate ion, methanesulfonate ion, p-toluenesulfonate ion, oleate ion, ibuprofen salt ion, or geraniate ion.

[0118] Preferably, the amino acid anion is selected from amino acid anions well known in the art, such as lactate ion, cysteine ​​ion, or glycine ion.

[0119] Preferably, the ester anion is selected from well-known ester anions in the art, such as hydrosulfide ions, dimethyl phosphonate ions, dibutyl phosphate ions, methyl sulfate ions, ethyl sulfate ions, or polyacrylamide anions.

[0120] Preferably, the cyano-containing anion is selected from dicyandiamide salt ions or thiocyanate ions, which are well known in the art.

[0121] Preferably, the halide metal salt anion is selected from well-known halide metal salt anions in the art, such as ferric chloride anion, aluminum chloride anion, titanium chloride anion, zinc chloride anion, or copper chloride anion.

[0122] In some specific embodiments of the present invention, the inorganic or organic anions preferably include one or more of the following fluorine-containing anions: tetrafluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate ion, trifluoromethanesulfonylimide ion, antimony hexafluoride ion, trifluoroacetate ion, etc.

[0123] In some specific embodiments of the present invention, the polymerizable monomer having an ionic liquid group is selected from 1-vinyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (VBImTFSI), 1-vinyl-3-methylimidazolium sulfate methyl ester, 1-vinyl-3-methylimidazolium iodide, 1-vinyl-3-methylimidazolium bromide, 1-vinyl-3-methylimidazolium chloride, 1-vinyl-3-methylimidazolium dimethyl phosphate, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-methylimidazolium hexafluoroantimonate, 1-vinyl-3-methylimidazolium trifluoromethanesulfonate, 1-vinyl-3-methylimidazolium perchlorate, 1-vinyl-3-methylimidazolium tetra ... Imidazole nitrate, 1-vinyl-3-methylimidazolium methanesulfonate, 1-vinyl-3-methylimidazolium p-toluenesulfonate, 1-vinyl-3-methylimidazolium acetate, 1-ethyl-3-vinylimidazolium bromide, 1-ethyl-3-vinylimidazolium iodide, 1-ethyl-3-vinylimidazolium ethyl sulfate, 1-ethyl-3-vinylimidazolium diethyl phosphonate, 1-ethyl-3-vinylimidazolium tetrafluoroborate, 1-ethyl-3-vinylimidazolium hexafluorophosphate, 1-ethyl-3-vinylimidazolium hexafluoroantimonate, 1-ethyl-3-vinylimidazolium nitrate, 1-ethyl-3-vinylimidazolium trifluoromethanesulfonate, 1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-vinylimidazolium Perchlorate, 1-Ethyl-3-vinylimidazolium thiocyanate, 1-Ethyl-3-vinylimidazolium methanesulfonate, 1-Ethyl-3-vinylimidazolium p-toluenesulfonate, 1-Ethyl-3-vinylimidazolium acetate, 1-Ethyl-3-vinylimidazolium trifluoroacetate, 1-Ethyl-3-vinylimidazolium hydrogen sulfate, 1-propyl-3-vinylimidazolium bromide, 1-propyl-3-vinylimidazolium iodide, 1-propyl-3-vinylimidazolium hexafluorophosphate, 1-propyl-3-vinylimidazolium hexafluoroantimonate, 1-propyl-3-vinylimidazolium nitrate, 1-propyl-3-vinylimidazolium trifluoromethanesulfonate, 1-propyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-propyl-3-vinylimidazolium perchlorate 1-Propyl-3-vinylimidazolium thiocyanate, 1-Propyl-3-vinylimidazolium methanesulfonate, 1-Propyl-3-vinylimidazolium p-toluenesulfonate, 1-Propyl-3-vinylimidazolium acetate, 1-Propyl-3-vinylimidazolium trifluoroacetate, 1-Butyl-3-vinylimidazolium chloride, 1-Butyl-3-vinylimidazolium bromide, 1-Butyl-3-vinylimidazolium tetrafluoroborate, 1-Butyl-3-vinylimidazolium hexafluorophosphate, 1-Butyl-3-vinylimidazolium trifluoromethanesulfonate, 1-Butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-Butyl-3-vinylimidazolium hydrogen sulfate, 1-Butyl-3-vinylimidazolium methanesulfonate, 1-Butyl-3-vinylimidazolium dibutyl phosphate salt1-Butyl-3-vinylimidazolium dicyandiamide, 1-Butyl-3-vinylimidazolium hexafluoroantimonate, 1-Butyl-3-vinylimidazolium nitrate, 1-Butyl-3-vinylimidazolium octylsulfonate, 1-Butyl-3-vinylimidazolium thiocyanate, 1-Butyl-3-vinylimidazolium p-toluenesulfonate, 1-benzyl-3-vinylimidazolium bromide, 1-benzyl-3-vinylimidazolium chloride, 1-benzyl-3-vinylimidazolium hexafluorophosphate, 1-benzyl-3-vinylimidazolium hexafluoroantimonate, 1-benzyl-3-vinylimidazolium tetrafluoroborate, 1-benzyl-3-vinylimidazolium methanesulfonate, 1-benzyl-3-vinylimidazolium trifluoromethanesulfonate One or more of the following: 1-benzyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)amide salt, 1-benzyl-3-vinylimidazolium hydrogen sulfate, 1-benzyl-3-vinylimidazolium nitrate, 1-benzyl-3-vinylimidazolium methanesulfonate, 1-benzyl-3-vinylimidazolium dicyandiamide salt, 1-benzyl-3-vinylimidazolium thiocyanate, 1-allyl-3-vinylimidazolium chloride, 1-allyl-3-vinylimidazolium bromide, 1-allyl-3-vinylimidazolium iodide, 1-allyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide salt, 1-allyl-3-vinylimidazolium hexafluorophosphate, and 1-allyl-3-vinylimidazolium tetrafluoroborate.

[0124] Preferably, the polymerizable monomer having ionic liquid groups in the slurry has a mass content of 5% to 70%, more preferably 20% to 40%.

[0125] This invention demonstrates through experiments that the slurry with the addition of the aforementioned polymerizable monomers has a relatively low oxygen content, resulting in a smaller inhibitory effect of oxygen on polymerization and a significantly shorter curing time. The prepared device exhibits a significantly reduced driving energy, while the fading time remains unaffected, the number of cycles increases significantly, and the overall cycle stability of the device is significantly improved. Furthermore, the polymeric cationic framework provides an electrostatic shielding effect, unifying the silver ion flux on the working electrode surface and promoting uniform silver deposition.

[0126] Preferably, the polymerizable monomer that can coordinate with metal ions is selected from one or more of N-vinylpyrrolidone (NVP), vinyltris(2-methoxyethoxy)silane, N,N'-methylenebisacrylamide, acrylamide, dimethoxydivinylsilane, dimethyl(dimethylamino)vinylsilane, triethoxy(1-phenylvinyl)silane, methylvinyldimethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.

[0127] The polymerizable monomer that can coordinate with metal ions has a mass content of 1% to 48% in the slurry, preferably 5% to 25%, and more preferably 5% to 10%.

[0128] The present invention adds polymerizable monomers that can coordinate with metal ions to the above slurry, which can not only inhibit the deposition and growth of dendrites on the entire surface of the device and control the area where dendrites are generated to be only at the edge of the device, but also significantly protect the electrodes from electrochemical corrosion damage, and greatly increase the number of cycles.

[0129] Preferably, when the polymerizable monomer is selected from polymerizable monomers that can coordinate with metal ions, the slurry may also include other olefin-containing monomers that do not have the ability to coordinate with metal ions.

[0130] The present invention does not specifically limit the type of monomer containing olefin groups, as long as it has olefin groups and can undergo polymerization reaction. Preferably, the monomer containing olefin groups includes one or more of acrylates, acrylics, and acryloyls.

[0131] The olefin-containing monomer in the slurry preferably contains 5% to 25% by mass, more preferably 10% to 20%.

[0132] Preferably, the polymerizable monomer of the present invention includes polymerizable monomers having ionic liquid groups and polymerizable monomers that can coordinate with metal ions.

[0133] The preferred ratio of the polymerizable monomer with ionic liquid groups to the polymerizable monomer that can coordinate with metal ions is 1:0.2 to 1:2, more preferably 1:0.2 to 1:0.5.

[0134] In some specific embodiments of the present invention, the polymerizable monomer includes 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt.

[0135] In some specific embodiments of the present invention, the polymerizable monomers include acrylic acid and N-vinylpyrrolidone.

[0136] In some specific embodiments of the present invention, the polymerizable monomers include hydroxyethyl methacrylate and N-vinylpyrrolidone.

[0137] In some specific embodiments of the present invention, the polymerizable monomers include 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and N-vinylpyrrolidone.

[0138] In some specific embodiments of the present invention, the polymerizable monomers include 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and vinyltris(2-methoxyethoxy)silane.

[0139] In some specific embodiments of the present invention, the polymerizable monomers include 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and N,N'-methylenebisacrylamide.

[0140] In some specific embodiments of the present invention, the polymerizable monomers include 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, N,N'-methylenebisacrylamide, and vinyltris(2-methoxyethoxy)silane.

[0141] The simultaneous addition of polymerizable monomers with ionic liquid groups and polymerizable monomers that can coordinate with metal ions can achieve a dual positive gain effect. This not only reduces the driving voltage and thus the operating current of the device, but also provides an electrostatic shielding effect through the polymerized cationic framework. This unifies the silver ion flux on the working electrode surface, and the framework containing silver ion complexation functional groups acts as a polymer inhibitor, thereby reducing and balancing the electroplating rate of the entire working electrode surface. This prevents dendritic deposition and growth, protects the electrode, improves the cycling stability of the device, and achieves a long life cycle of more than 8,000 cycles.

[0142] Preferably, the slurry also includes additives.

[0143] The additives include, but are not limited to, one or more of diluents, leveling agents, and crosslinking agents.

[0144] The diluent preferably comprises 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-butyl-3-methylimidazolium chloride) (BMImCl), 1-n-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-n-butyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide, (1-ethyl-3-methylimidazolium chloride), (1-butyl-3-methylimidazolium bromide), (1-ethyl-3-methylimidazolium bromide), (1-ethyl-3-methylimidazolium chloride ... 1-Butyl-2,3-dimethylimidazolium, 1,2-dimethyl-3-hydroxyethylimidazolium p-toluenesulfonate, 1,2-dimethyl-3-hydroxyethylimidazolium bis(trifluoromethanesulfonylimide), 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, trimethylhydroxyethylamine bis(trifluoromethanesulfonyl)imide, N-octylpyridine hydrogen sulfate, N-octylpyridine perchlorate, N-hexylpyridine bromide, trimethylhydroxyethylimidazolium chloride Benzylamine, N-methylethylpiperidine bromide, N-methylbutylpiperidine bis(trifluoromethanesulfonyl)imide salt, (N-methylbutylpyrrolidine) chloride, (N-methylbutylpyrrolidine) bromide, N-methylethylmethanesulfonate, methylethylmorpholine bromide, N-methylpropylmorpholine bis(trifluoromethanesulfonyl)imide salt, methyltributylphosphine tetrafluoroborate, methyltributylphosphine hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-epoxypropyl-3-methyl) The following are some of the following: (1-carboxymethyl-3-methylimidazolium chloride), 1-epoxypropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-carboxymethyl-3-methylimidazolium chloride), N-sulfonic acid butyl-3-methylimidazolium hydrogen sulfate, (1-acetonitrile-3-methylimidazolium chloride), 1-butyl-3-methylimidazolium hydroxide, 1-(propyltriethoxy)-3-methylimidazolium chloride, dimethyl sulfoxide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate and dioctyl phthalate.

[0145] The mass content of the diluent in the slurry is preferably 30% to 95%, more preferably 50% to 70%.

[0146] The present invention preferably uses a compound containing bis(trifluoromethanesulfonyl)imide as a diluent, which reduces the amount of chlorinated (1-butyl-3-methylimidazolium) added to the system. The bis(trifluoromethanesulfonyl)imide anion brings hydrophobic and low dissolved oxygen properties, which greatly shortens the curing time of the slurry and makes the device have better electrodeposition color change performance and cycle stability.

[0147] The leveling agent preferably includes one or more of the following: polyethylene glycol, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), hydroxyethyl cellulose, N,N-diethylpropynylamine sulfate, polyacrylic acid, polystyrene, poly(sodium 4-styrene sulfonate and maleic acid) copolymer, copolymer of 1-vinylimidazolium and 1,4-butanediol glycidyl ether, and fatty acid quaternary ammonium salts.

[0148] The leveling agent is preferably present in the slurry at a mass content of 0.5% to 10%, more preferably 0.5% to 5%.

[0149] Preferably, the slurry also includes a crosslinking agent.

[0150] The crosslinking agent preferably includes one or more of polyethylene glycol diacrylate (PEGDA), ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.

[0151] The crosslinking agent in the slurry preferably has a mass content of 0.2% to 5%, more preferably 0.2% to 1.5%.

[0152] In some specific embodiments of the present invention, the additive includes chlorinated (1-butyl-3-methylimidazole).

[0153] In some specific embodiments of the present invention, the additive includes 1-n-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide and chlorinated (1-butyl-3-methylimidazolium).

[0154] The mass ratio of 1-n-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide to chloride (1-butyl-3-methylimidazolium) is preferably 0.5:1 to 10:1, more preferably 2:1 to 4:1.

[0155] In some specific embodiments of the present invention, the additive includes 1-n-butyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide and chlorinated (1-butyl-3-methylimidazolium).

[0156] The mass ratio of 1-n-butyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide to chloride (1-butyl-3-methylimidazolium) is preferably 0.5:1 to 10:1, more preferably 2:1 to 4:1.

[0157] Preferably, the metal source is selected from one or more of silver chloride, silver bis(trifluoromethanesulfonyl)imide, silver oxide, silver bromide, silver sulfate, silver perchlorate, silver nitrate, and silver iodide.

[0158] The mass content of the metal source in the slurry is preferably 0.5% to 15%, more preferably 1% to 5%.

[0159] Preferably, the initiator is selected from thermal initiators or photoinitiators.

[0160] The thermal initiator preferably includes one or more of azobisisobutyronitrile (AIBN), benzoyl peroxide, persulfate, di-tert-butyl peroxide, benzoyl peroxide, and thiobenzoyl.

[0161] The photoinitiator preferably includes photoinitiator 2959, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide (TPO), photoinitiator 184, TPO-L, photoinitiator 1173, photoinitiator 907, photoinitiator 369, photoinitiator 1490, photoinitiator 1700, diazonium salt, diaryliodomonium salt, triarylthionium salt, alkylthionium salt, iron aromatic salt, sulfonyloxyketone, triarylsiloxane, benzoin, benzoin dimethyl ether, benzoin ethyl ether, and benzoin isopropyl benzoate. One or more of the following: ether, benzoyl ether, diphenyl ethyl ketone, α,α-dimethoxy-α-phenylacetophenone, α,α-diethoxyacetophenone, α-hydroxyalkyl phenyl ketone, α-aminealkyl phenyl ketone, aromatic phosphine oxide, bisbenzoylphenylphosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, michidone, thiopropoxythoxanthone, isopropylthoxanthone, fluorinated diphenyltitane, bis(pentafluorophenyl)titane, or lithium phenyl(2,4,6-trimethylbenzoyl)phosphate (LAP).

[0162] The initiator in the slurry preferably contains 0.5% to 5% by mass, more preferably 1% to 3%.

[0163] The slurry provided by this invention is suitable for integrated electrochromic devices, especially flexible thin film devices. It can be rapidly cured and polymerized in situ in an air environment to form an active layer, i.e., the integrated electrochromic layer of the device. The visible light transmittance of the prepared large-area flexible electrochromic device can drop from 65% to below 5% within five minutes, and it exhibits high infrared and ultraviolet reflectivity (>99.7%). It also has excellent uniformity and excellent cycling stability and durability in a room temperature air environment (cycle count >8000 times), a wide operating temperature range (-20 to 100℃), and excellent bistable performance (color retention time in open circuit state >7 days).

[0164] Based on this, the present invention provides an integrated electrochromic device, comprising a first substrate layer, a working electrode layer, an integrated electrochromic layer, a counter electrode layer, and a second substrate layer.

[0165] The integrated electrochromic layer is formed by curing the above-mentioned slurry.

[0166] The present invention does not have any special limitation on the material of the first substrate layer and the second substrate layer, and can be any substrate material known to those skilled in the art.

[0167] The materials and thicknesses of the first and second base layers are as described above and will not be repeated here.

[0168] The material of the working electrode is as described above and will not be repeated here.

[0169] In some specific embodiments of the present invention, the working electrode layer is Au-ITO-PET.

[0170] In this invention, the conductive layer material of the counter electrode is selected from a transparent conductive metal electrode.

[0171] The material of the counter electrode is as described above and will not be repeated here.

[0172] In some specific embodiments of the present invention, the counter electrode layer is a grooved PET film of organic silver paste.

[0173] This invention uses a transparent conductive metal electrode as the counter electrode, which can play a role in electron transport and participate in redox while ensuring the transparency of the device. Based on this, this invention has prepared an integrated transparent electrochromic device.

[0174] The preparation methods for the counter electrode and the working electrode have been described above and will not be repeated here.

[0175] The present invention does not impose any special limitation on the thickness of the working electrode layer and the counter electrode layer, and can be as described above, and will not be repeated here.

[0176] The aforementioned devices can be flexible devices, specifically dynamically modulated flexible films based on reversible metal electrodeposition (RME) that can be adhered to glass surfaces. These films are expected to overcome challenges related to cost, color, contrast, and durability, enabling broader control over visible light and solar radiation. Furthermore, existing ordinary glass, such as architectural glass, automotive window glass, and household glass, can be directly converted into RME glass through methods such as film application or film lamination, offering enormous application potential.

[0177] This invention employs a polymeric ionic liquid as the polymeric framework of the gel, combined with an ionic liquid electrolyte. Firstly, it reduces the driving potential and improves the kinetics of electrochemical deposition. The polymeric cationic framework provides an electrostatic shielding effect, unifying the silver ion flux on the working electrode surface and promoting uniform silver deposition, reducing the deposition current and plating rate. This reduces degradation (such as degradation caused by material, electrolyte, or ion trapping) and dendritic metal deposition growth, and achieves uniform and dense deposition of large-area devices. Compared to inert polymeric framework electrolytes, such as acrylate-based or polyurethane-based electrolytes, the driving potential is reduced from 0.6V to 0.28V. Secondly, the particularly preferred hydrophobic ionic liquid allows the electrodeposited device to maintain relatively stable performance even in humid environments. Thirdly, the low viscosity and good wettability of the polymeric electrolyte precursor facilitates large-scale device production. When adding or extruding the electrolyte into the electrodeposition device container, it avoids the formation of trapped air bubbles during manufacturing, which can lead to poor contact between the electrolyte and electrode interface. Fourthly, due to the low oxygen solubility of the ionic liquid electrolyte, it can achieve rapid photocuring in-situ polymerization in air. Compared to traditional photocurable inert electrolyte layers, such as the photocrosslinking of acrylate-based ionic gel electrolytes, whose curing requires a constant supply of inert gas in an inert chamber for smooth and rapid curing, and compared to thermosetting polymerized gel electrolytes, which typically require a large amount of heat or long curing times, photopolymerization is easier and requires less energy. Fifth, thanks to the excellent thermal stability of polymeric ionic gels, especially the preferred use of weakly coordinated or uncoordinated bis(trifluoromethanesulfonyl)imide (TFSI) anions, due to their large molecular size, strong charge delocalization, and relatively weak binding with cations, they not only have high conductivity but also a lower solidification temperature than conventional counterions, allowing electrodeposition devices to operate over a wide temperature range (-20 to 100°C). Sixth, the polymeric ionic liquid's polymeric framework forms an anti-cation protective layer on the electrode surface, which to some extent delays the dissolution of elemental silver in the open-circuit state. Furthermore, the presence of only zero-valent silver and +1 valent silver ions in the electrolyte system gives the product excellent bistable performance, maintaining its colored state for >7 days in the open-circuit state. Theoretically, the amount of Ag deposited on the working electrode is the same as the amount of Ag dissolved on the counter electrode. As long as Ag... + / Ag is the only redox pair, thus achieving bistable operation because the deposited Ag layer is not corroded by any amount of electrolyte. Seventh, by specifically selecting bis(trifluoromethanesulfonyl)imide (TFSI) anions to replace most of the chloride ions, the content of chloride ions that can coordinate with the working electrode gold in the gel electrolyte layer is greatly reduced, thereby increasing the threshold of the electrochemical reaction of gold. This allows for fading with a higher voltage while ensuring that the working electrode of the gold film is not electrochemically damaged, and reducing the fading time.

[0178] On the other hand, by polymerizing a sufficient number of functional groups (such as hydroxyl, carbonyl, or amide groups) that have a strong affinity for silver ions onto the electrolyte polymer backbone, a silver ion supply layer with uniformly distributed silver adsorption sites is formed on the electrode surface. This acts as a conventional polymer inhibitor in gel systems where high molecular weight polymers cannot diffuse smoothly. It has three main functions: First, by inducing a uniform electroplating rate on the electrode surface and inhibiting dendritic metal deposition growth through adsorption mechanisms, it promotes the formation of a smooth and dense metal film that can effectively regulate light. Without the abundant silver adsorption sites on these polymeric electrolytes, local electric fields would form at inhomogeneities, resulting in dendritic electrodeposition. The polymer layer polarizes the electrode and introduces an additional nucleation energy barrier (i.e., increased overpotential). Since metal ions must diffuse through the charged polymer layer and compete with the polymer for adsorption sites on the electrode surface, the deposition rate is reduced, making electroplating more uniform. Second, it enables uniform color change over a larger area. Due to the deposition of a continuous and dense metal film, the electrode resistance of the device decreases as the metal film thickens. The continuous and uninterrupted state of the metal film significantly increases the electrode conductivity during coloring. Essentially, this achieves uniform coloring of large-area devices by reducing the sheet resistance of the electrodes. However, in electrolytes without silver ion deposition sites, the metal electrodeposit is microscopically isolated and discontinuous, failing to significantly reduce electrode conductivity. Thirdly, polymeric ionic electrolyte gels containing numerous silver adsorption sites greatly improve the durability of the metal-organic slurry mesh for the electrodes by promoting uniform electroplating on the electrode mesh and limiting side reactions that degrade the mesh during cycling.

[0179] This invention also provides a method for fabricating the above-mentioned reflective integrated electrochromic device, comprising the following steps:

[0180] S1) Apply the integrated electrochromic layer solution or slurry to the surface of the counter electrode or working electrode, seal the film and solidify the solution or slurry;

[0181] S2) Laser slicing, electrode attachment, and encapsulation yield a reflective integrated electrochromic device;

[0182] Or it may include the following steps:

[0183] S11) Drill pre-drilled holes on a rigid conductive substrate, attach the working electrode plate and the counter electrode plate face to face, and use spacers to control the plate spacing to form a hollow device shell.

[0184] S22) Inject the integrated electrochromic layer solution or slurry into the hollow device shell through the aforementioned pre-formed holes;

[0185] S33) Dispensing and sealing to solidify the solution or slurry, resulting in a reflective integrated electrochromic device.

[0186] This invention also provides a method for preparing the above-mentioned solvent-free acrylate electrochromic device, comprising the following steps: S1) mixing a metallic silver compound component, a polymerizable monomer, and an additive to obtain an electrochromic slurry; the polymerizable monomer includes a hydrophobic polymeric monomer of acrylate type; the additive includes an ionic liquid; the ionic liquid molecule structure contains hydrophobic long alkyl and / or aryl functional groups; S2A) coating the electrochromic slurry onto the surface of the working electrode layer or the counter electrode layer, then combining it with the counter electrode layer or the working electrode layer, and curing it to obtain a solvent-free acrylate electrochromic device; or, S2B) ... A hollow device is provided; the hollow device includes a rigid first substrate and a rigid second substrate arranged face to face, a working electrode layer is provided on the side of the rigid first substrate and the rigid second substrate facing each other, and a counter electrode layer is provided on the side of the rigid second substrate facing the rigid first substrate, with a spacer controlling the spacing between the working electrode layer and the counter electrode layer; a pre-formed hole is provided on the rigid first substrate or the rigid second substrate, and the hollow device is a closed device except for the pre-formed hole; the electrochromic slurry is injected between the working electrode and the counter electrode of the hollow device through the pre-formed hole and cured to obtain a solvent-free acrylate system electrochromic device.

[0187] In this invention, there are no special restrictions on the source of all raw materials; they can be commercially available. The metallic silver compound components, polymerizable monomers, and additives are all as described above and will not be repeated here.

[0188] The electrochromic paste is obtained by mixing the metallic silver compound component, polymerizable monomer and additive; the mixing method can be any method known to those skilled in the art and there are no special restrictions, as long as the mixture is uniform.

[0189] The electrochromic paste is applied to the surface of the working electrode layer or the counter electrode layer, and then composited with the counter electrode layer or the working electrode layer and cured. The working electrode layer and the counter electrode layer are preferably composited on the surface of the first substrate layer and the surface of the second substrate layer, respectively. The curing method is any curing method known to those skilled in the art and there are no special limitations. In this invention, ultraviolet curing is preferred. After curing, laser slicing, electrode attachment, and encapsulation are preferred to obtain a solvent-free acrylate system electrochromic device.

[0190] Alternatively, the electrochromic paste can be injected between the working electrode and the counter electrode of the hollow device; in this case, the working electrode and the counter electrode are respectively bonded to the surface of the first substrate layer and the surface of the second substrate layer; the first substrate layer and the second substrate layer are rigid substrates; the working electrode and the counter electrode of the hollow device are arranged face to face, and more specifically, the distance between the working electrode and the counter electrode of the hollow device can be controlled by spacers; in a specific embodiment provided by the present invention, the hollow device is preferably prepared by the following method: pre-drilling holes in a rigid conductive substrate, bonding the working electrode plate and the counter electrode plate face to face, and using spacers to control the plate spacing to form a hollow device; the electrochromic paste is preferably injected through the pre-drilled holes of the hollow device, and after injection, it is preferably sealed with adhesive and cured to obtain a solvent-free acrylate system electrochromic device; the curing method can be any curing method known to those skilled in the art, and there are no special limitations, but ultraviolet curing is preferred in the present invention.

[0191] The reflective integrated electrochromic device provided by this invention has the advantages of being transparent and having a long steady-state time, and can be used in fields such as skylights and windows.

[0192] Compared with the prior art, the present invention provides a reflective integrated electrochromic device, comprising, in sequence: a first substrate layer, a counter electrode layer, an integrated electrochromic layer, a working electrode layer, and a second substrate layer; the integrated electrochromic layer comprises a metal source compound; the metal source compound is selected from one or more of the following: silver chloride, silver acetate, silver nitrate, silver perchlorate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, silver bis(trifluoromethanesulfonyl)imide, copper fluoride, copper chloride, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, gold chloride, gold sulfide, nickel chloride, nickel sulfate, cobalt chloride, and platinum chloride.

[0193] This invention electrochemically deposits a thin metal film inside the device. When natural light shines on the metal film from one side, most of the light is reflected to the same side. Therefore, the reflective device can both adjust the color of visible light and block the radiant energy (including visible and near-infrared light) generated by the light from the incident light. Silver and copper are two metals with high reflectivity, making them very suitable for reflective devices. However, silver and copper (especially silver) compounds often have poor solubility, making high-concentration electrodeposition impossible. Furthermore, conventional solvents dissolve silver and copper compounds with very poor stability, causing the device to fail after several fading cycles. This invention uses a special metal ion liquid formulation system that can dissolve large amounts of poorly soluble silver and copper compounds. The resulting complex effectively protects the long-term stability of silver and copper ions, ensuring stable fading even after 10,000 cycles of cyclic fatigue testing and maintaining color for 5,000 hours in an open-circuit state. Furthermore, the transparent electrode structure used in this invention can ensure that the dynamic range of transmittance in the visible light range (380-780nm) is greater than 66%, and the dynamic range of reflectance in the visible light and near-infrared range (380-2500nm) is greater than 70%, which can simultaneously manage light and heat, such as controllable privacy film, controllable heat insulation film, etc. Attached Figure Description

[0194] Figure 1 is a schematic diagram of the structure of the reflective integrated electrochromic device provided by the present invention;

[0195] Figure 2 is a schematic diagram of the transmittance test sampling points of the electrochromic devices obtained in Examples 10-12 and Comparative Examples 5-7 of the present invention during the cycling process.

[0196] Figure 3 is a schematic diagram of the cyclic voltammetry curve of the electrochromic device;

[0197] Figure 4 is a schematic diagram of dendrite growth on the entire surface of the working electrode of the flexible device.

[0198] Figure 5 is a schematic diagram showing the absence of dendrite growth on the surface of the working electrode of the flexible device.

[0199] Figure 6 is a schematic diagram of the complete solid line state of the silver mesh of the organic silver paste film on the electrode of the flexible device;

[0200] Figure 7 is a schematic diagram showing the damaged and broken silver mesh of the organic silver paste film on the electrode of the flexible device.

[0201] Figure 8 is a physical image of the device of Example 24B with a visible light transmittance of 65% in the faded state;

[0202] Figure 9 is a physical image of the device of Example 24B with the colored state colored to 5%;

[0203] Figure 10 shows the fading spectrum of the device in Example 24B. Detailed Implementation

[0204] To further illustrate the present invention, the reflective integrated electrochromic device and its fabrication method provided by the present invention are described in detail below with reference to embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims.

[0205] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods well known to those skilled in the art. The polyethylene glycol diacrylate used in the examples has a molecular weight of 575.

[0206] Example 1

[0207] S1 is a mixture of 0.3g silver chloride, 5g 1-butyl-3-methylimidazolium chloride, 3g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.01g lithium phenyl (2,4,6-trimethylbenzoyl)phosphate and 0.1g vinylsiloxane;

[0208] S2 adds 0.03g of spacers (the spacers are spherical in shape, made of polyacrylic acid resin, with a particle size of 50μm, 100μm or 200μm) to the mixed solution and stirs it evenly. Then, it is quickly coated onto the surface of the PET-ITO-Au composite conductive film of the working electrode by a two-roller coating method to form an electrochromic layer.

[0209] S3 combines the counter electrode silver mesh film with the coated PET-ITO-Au composite conductive film and cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0210] S4 roller slicing, electrode attachment, and encapsulation yield a flexible, photo-solid-state electrochromic device.

[0211] When the transmittance of the transparent substrate is greater than 95%, the average transmittance and reflectance data of the colored and uncolored electrochromic layers of different thicknesses in the visible and near-infrared range (380–2500 nm) are shown in Table 1 below. The transmittance was measured according to the method in GB / T2680-2021 "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Architectural Glass", and the reflectance was measured according to the method in GB / T 33234-2016 "Test Method for Reflectance of Solar Thermal Power Generation Glass Mirrors". The dynamic range of reflectance in the visible and near-infrared range is the difference between the reflectance in the colored state and the reflectance in the uncolored state in the 380–2500 nm range.

[0212] Table 1

[0213] Under the condition of an active area of ​​100mm*100mm, the coloring time and fading time of electrochromic layers of different thicknesses are shown in Table 2 below. The method for determining the coloring time and fading time is as follows: The above electrochromic devices are placed in a UV-Vis spectrometer, and the maximum and minimum transmittance values ​​are detected at 550nm. The time taken for the transmittance to change from the maximum value to the minimum value is recorded as the coloring time, and the time taken for the transmittance to change from the minimum value to the maximum value is recorded as the fading time.

[0214] Table 2

[0215] The device's colored state can maintain its color for 5000 hours at room temperature without fading. After 10,000 fading cycles (±0.6V), the reflectance remains consistent with the initial state, maintaining a reflectance of >98% in the colored state and 25% in the uncolored state. The device's visible light (380–780nm) transmittance dynamically varies by 78%, and its visible and near-infrared (380–2500nm) reflectance dynamically varies by 73%.

[0216] Example 2

[0217] S1 is a mixture of 0.5g silver chloride, 6g 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, 2g acrylic acid, 1g N,N'-methylenebisacrylamide, 0.01g 2-hydroxy-2-methylphenylacetone, 0.005g hydroquinone, and 0.1g γ-glycidoxypropyltrimethoxysilane.

[0218] S2 adds 0.04g of spacers (the spacers are spherical in shape, made of silicon dioxide, and have a particle size of 50μm, 100μm or 200μm) to the mixed solution and stirs it evenly. Then, it is quickly coated on the surface of the counter electrode nano silver film by a double roller coating method to form an electrochromic layer.

[0219] S3 combines the working electrode PET-ITO-Pt composite conductive film with the counter electrode nano silver film, and then cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0220] S4 molding, slicing, electrode attachment, and encapsulation yield a flexible, photo-solid-state electrochromic device.

[0221] When the transmittance of the transparent substrate is greater than 95%, the average transmittance and reflectance data of the colored and uncolored states of the electrochromic layer of different thicknesses in the visible and near-infrared range (380-2500nm) are shown in Table 3 below. The test method is the same as that in Example 1.

[0222] Table 3

[0223] Under the condition of an active area of ​​100mm*100mm, the coloring time and fading time of electrochromic layers of different thicknesses are shown in Table 4 below. The test method is the same as that in Example 1.

[0224] Table 4

[0225] The device's colored state can maintain its color for 5000 hours at room temperature without fading. After 10,000 fading cycles (±0.6V), the reflectance remains consistent with the initial state, maintaining a reflectance of >98% in the colored state and 10% in the uncolored state. The device's visible light (380–780nm) transmittance dynamically varies by 85%, and its visible and near-infrared (380–2500nm) reflectance dynamically varies by 88%.

[0226] Example 3

[0227] S1 is a mixture of 0.6g bis(trifluoromethanesulfonyl)imide silver, 5g N-butylpyridine hexafluorophosphate, 5g ethylene glycol monoethyl ether, 0.1g aminosiloxane, 2g acrylate polyol, 0.1g isophorone diisocyanate, 0.01g dibutyltin diacetate, and 0.2g lithium nitrate.

[0228] S2 adds 0.03g of spacers (the spacers are spherical in shape, made of polystyrene resin, with a particle size of 50μm, 100μm or 200μm) to the mixed solution and stirs it evenly. Then, it is quickly coated onto the surface of the PET-Pt composite conductive film of the working electrode by a two-roller coating method to form an electrochromic layer.

[0229] S3 combines the working electrode PET-Pt composite conductive film with the counter electrode PET-ITO-Ag composite conductive film, and accelerates the curing of the electrochromic slurry by heating.

[0230] S4 laser slicing, electrode attachment, and encapsulation yield a thermosetting flexible integrated gel electrochromic device.

[0231] When the transmittance of the transparent substrate is greater than 95%, the average transmittance and reflectance data of the colored and uncolored states of the electrochromic layer of different thicknesses in the visible and near-infrared range (380-2500nm) are shown in Table 5 below. The test method is the same as that in Example 1.

[0232] Table 5

[0233] Under the condition of an active area of ​​100mm*100mm, the coloring time and fading time of electrochromic layers of different thicknesses are shown in Table 6 below. The test method is the same as that in Example 1.

[0234] Table 6

[0235] The device's colored state can maintain its color for 5000 hours at room temperature without fading. After 10,000 fading cycles (±0.6V), the reflectance remains consistent with the initial state, maintaining a reflectance of >98% in the colored state and 28% in the uncolored state. The device's visible light (380–780nm) transmittance dynamically varies by 72%, and its visible and near-infrared (380–2500nm) reflectance dynamically varies by 70%.

[0236] Example 4

[0237] S1 uses a laser to cut injection holes in ITO glass, applies adhesive, and attaches the working electrode ITO and the counter electrode conductive silver glass face to face. Spacers (spherical in shape, made of polyacrylic acid resin, with a particle size of 200 μm) or spacer strips (strip-shaped, with a thickness of 500 μm or 3000 μm) are used to control the distance between the two electrode surfaces to be 200 μm, 500 μm, or 3000 μm.

[0238] S2 mixes 0.5g copper chloride, 5g 1-butyl-3-methylimidazolium chloride, 2g polyethylene glycol 1000, and 0.2g lithium nitrate;

[0239] S3 injects the solution into the device through a pre-made hole in the conductive glass;

[0240] S4 dispensing and sealing yields a rigid, integrated liquid electrochromic device.

[0241] When the transmittance of the transparent substrate is greater than 95%, the average transmittance and reflectance data of the colored and uncolored states of the electrochromic layer of different thicknesses in the visible and near-infrared range (380-2500nm) are shown in Table 7 below. The test method is the same as that in Example 1.

[0242] Table 7

[0243] Under the condition of an active area of ​​100mm*100mm, the coloring time and fading time of electrochromic layers of different thicknesses are shown in Table 8 below. The test method is the same as that in Example 1.

[0244] Table 8

[0245] The device's colored state can maintain its color for 1000 hours at room temperature without fading. After 10,000 fading cycles (±0.4V), the reflectance remains consistent with the initial state, maintaining a reflectance of >85% in the colored state and 10% in the uncolored state. The device's visible light (380–780 nm) transmittance exhibits a dynamic variation range of greater than 66%, while the visible and near-infrared (380–2500 nm) reflectance exhibits a dynamic variation range of 75%.

[0246] Example 5

[0247] S1 is a mixture of 0.1g nickel chloride, 0.2g silver chloride, 5g 1-butyl-3-methylimidazolium chloride, 3g acrylic acid, 1g ethylene glycol dimethacrylate, 0.01g lithium phenyl (2,4,6-trimethylbenzoyl)phosphate and 0.1g vinylsiloxane;

[0248] S2 adds 0.03g of spacers (the spacers are spherical in shape, made of polyacrylic acid resin, with a particle size of 50μm, 100μm or 200μm) to the mixed solution and stirs it evenly. Then, it is quickly coated onto the surface of the working electrode PET-Au composite conductive film by a two-roller coating method to form an electrochromic layer.

[0249] S3 combines the screen-printed silver mesh film on the electrode with the coated PET-Au composite conductive film, and then cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0250] S4 roller slicing, electrode attachment, and encapsulation yield a flexible, photo-solid-state electrochromic device.

[0251] When the transmittance of the transparent substrate is greater than 95%, the average transmittance and reflectance data of the colored and uncolored electrochromic layers of different thicknesses in the visible and near-infrared range (380-2500nm) are shown in Table 9 below. The transmittance was measured according to the method in GB / T2680-2021 "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Parameters of Architectural Glass", and the reflectance was measured according to the method in GB / T 33234-2016 "Test Method for Reflectance of Solar Thermal Power Generation Glass Mirrors".

[0252] Table 9

[0253] Under the condition of an active area of ​​100mm*100mm, the coloring time and fading time of electrochromic layers of different thicknesses are shown in Table 10 below. The method for determining the coloring time and fading time is as follows: The above electrochromic devices are placed in a UV-Vis spectrometer, and the maximum and minimum transmittance values ​​are detected at 550nm. The time taken for the transmittance to change from the maximum value to the minimum value is recorded as the coloring time, and the time taken for the transmittance to change from the minimum value to the maximum value is recorded as the fading time.

[0254] Table 10

[0255] The device's colored state can maintain its color for 5000 hours at room temperature without fading. After 10,000 fading cycles (±0.6V), the reflectance remains consistent with the initial state, maintaining a reflectance of >98% in the colored state and 23% in the uncolored state. The device's visible light (380–780nm) transmittance exhibits a dynamic variation range of greater than 62%, while its visible and near-infrared (380–2500nm) reflectance exhibits a dynamic variation range of 75%.

[0256] Example 6

[0257] S1 is made by mixing 0.5g silver nitrate, 5g 1-dodecyl-3-methylimidazolium chloride, 4g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.01g lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, 5g propylene carbonate, 0.1g vinylsiloxane, and 1g polyglycerol 10.

[0258] S2 adds 0.03g of spacers (spherical in shape, made of polyacrylic acid resin, with a particle size of 100μm) to the mixed solution, stirs until uniform, and then quickly coats the working electrode PET-ITO-Au composite conductive film using a two-roller coating method.

[0259] S3 combines the counter electrode silver mesh film with the coated PET-ITO-Au composite conductive film and cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0260] S4 roller slicing, electrode attachment, and encapsulation yielded a flexible photo-solid integrated gel electrochromic device with an active area of ​​100mm*100mm and an electrochromic layer thickness of 100μm.

[0261] Comparative Example 1

[0262] Replace the 1-dodecyl-3-methylimidazolium chloride in step S1 of Example 6 with 1-butyl-3-methylimidazolium chloride, and otherwise remain the same as in Example 6.

[0263] The current and reflectance variations in the visible and infrared ranges (380–2500 nm) of the devices prepared using ionic liquids with different carbon chains in Example 6 and Comparative Example 1 during the cycling process are shown in Table 11 below. The reflectance was measured according to the method in GB / T 33234-2016 "Test Method for Reflectance of Photothermal Power Generation Glass Mirrors". The device cycling steps were as follows: 1. Charge calculation: The device was first colored under a voltage of -1V, and the cycle stopped when the reflectance change reached 25%, recorded as Q. 2. Cyclic coloring stage: The voltage was -1V, and the cycle stopped when the charge integrated to Q. 3. Cyclic rest stage: The voltage was 0V for 30 seconds. 4. Cyclic fading stage: The voltage was +0.3V, and the cycle stopped when the charge integrated to Q. In Table 11, the current is the current of the device after the corresponding number of cycles when colored for 30 seconds under a voltage of -1V. The results show that adjusting the carbon chain length can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0264] Table 11

[0265] The coloring and fading times were determined as follows: the electrochromic devices were placed in a UV-Vis spectrometer, and the maximum and minimum transmittance values ​​were measured at 550 nm. The time taken for the transmittance to change from the maximum to the minimum was recorded as the coloring time, and the time taken for the transmittance to change from the minimum to the maximum was recorded as the fading time. The coloring and fading times for different cycles are shown in Table 12.

[0266] Table 12

[0267] Table 12 shows that when the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring and fading times of devices prepared with ionic liquids of different chain lengths vary during cycling. The coloring and fading times of long-chain ionic liquids are more stable, which reduces the difficulty of circuit control and packaging, laying the foundation for large-scale industrial production.

[0268] Example 7

[0269] S1 is a mixture of 0.5g silver bromide, 6g 1-vinyl-3-hexylimidazolium trifluoromethanesulfonylimide salt, 5g acrylic acid, 1g N,N'-methylenebisacrylamide, 0.01g 2-hydroxy-2-methylphenylacetone, 0.005g hydroquinone, and 0.1g γ-glycidoxypropyltrimethoxysilane.

[0270] S2 adds 0.04g of spacers (the spacers are spherical in shape, made of silicon dioxide, and have a particle size of 100μm) to the mixed solution, stirs it evenly, and then quickly coats it onto the counter electrode nano-silver film using a double roller coating method.

[0271] S3 combines the working electrode PET-ITO-Pt composite conductive film with the counter electrode nano silver film, and then cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0272] S4 molding, slicing, electrode attachment, and encapsulation yielded a flexible photo-solid-state electrochromic device with an active area of ​​100mm*100mm and an electrochromic layer thickness of 100μm.

[0273] Comparative Example 2

[0274] Replace the 1-vinyl-3-hexylimidazolium trifluoromethanesulfonylimide salt in step S1 of Example 7 with 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, otherwise the same as in Example 7.

[0275] The differences in current and reflectance in the visible and infrared ranges (380–2500 nm) during cycling for devices prepared with different carbon chain ionic liquids are shown in Table 13 below. The test method is the same as in Example 6. Table 13 shows that adjusting the length of the carbon chain can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0276] Table 13

[0277] The coloring and fading times of ionic liquids with different chain lengths are shown in Table 14 below. The test method is the same as that in Example 6.

[0278] Table 14

[0279] Table 14 shows that when the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring time and fading time of devices prepared with ionic liquids of different chain lengths vary during cycling. The time of long-chain ionic liquids is more stable, which also reduces the difficulty of circuit control and packaging.

[0280] Example 8

[0281] S1 is a mixture of 0.6g bis(trifluoromethanesulfonyl)imide silver, 5g N-eicosylpyridine hexafluorophosphate, 5g ethylene glycol monoethyl ether, 0.1g aminosiloxane, 2g acrylate polyol, 0.1g isophorone diisocyanate, 0.01g dibutyltin diacetate, and 0.2g lithium nitrate.

[0282] S2 adds 0.03g of spacers (spherical in shape, made of polystyrene resin, with a particle size of 100μm) to the mixed solution, stirs until homogeneous, and then rapidly coats the working electrode PET-ITO-Pt composite conductive film using a two-roller coating method.

[0283] S3 combines the working electrode PET-ITO-Pt composite conductive film with the counter electrode PET-ITO-Ag composite conductive film, and accelerates the curing of the electrochromic slurry by heating.

[0284] S4 laser slicing, electrode attachment, and encapsulation yielded a thermosetting flexible integrated gel electrochromic device with an active area of ​​100mm*100mm and an electrochromic layer thickness of 100μm.

[0285] Comparative Example 3

[0286] Replace N-eicosylpyridine hexafluorophosphate in step S1 of Example 8 with N-butylpyridine hexafluorophosphate, otherwise the same as in Example 8.

[0287] Table 15 below shows the reflectance difference and current variation data of devices prepared with different carbon chain ionic liquids in the colored and uncolored states in the visible and near-infrared range (380–2500 nm). The test method is the same as in Example 6. Table 15 shows that adjusting the length of the carbon chain can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0288] Table 15

[0289] When the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring and fading times of ionic liquids with different chain lengths are shown in Table 16 below. The test method is the same as in Example 6.

[0290] Table 16

[0291] Table 16 shows that, under simple packaging conditions, the coloring and fading times of devices prepared with ionic liquids of different chain lengths vary during cycling. The time of long-chain ionic liquids is more stable, which also reduces the difficulty of circuit control and packaging.

[0292] Example 9

[0293] S1 uses a laser to cut injection holes in ITO glass, applies adhesive, and attaches the working electrode ITO and the counter electrode conductive silver glass face to face. Spacers (spherical in shape, made of polyacrylic acid resin, with a particle size of 200 μm) or spacer strips (strip-shaped, with a thickness of 200 μm) are used to control the distance between the two electrode surfaces to 200 μm.

[0294] S2 mixes 0.5g of bis(trifluoromethanesulfonyl)imide silver, 5g of 1-dodecyl-3-methylimidazolium trifluoromethanesulfonylimide salt, 5g of hydroxyethyl methacrylate, 2g of polyethylene glycol 1000, and 0.2g of lithium nitrate.

[0295] S3 injects the solution into the device through a pre-made hole in the conductive glass;

[0296] S4 dispensing and sealing, UV curing, to obtain a photocurable rigid gel electrochromic device with an active area of ​​100mm*100mm and a thickness of 100μm for the electrochromic layer.

[0297] Comparative Example 4

[0298] Replace the 1-dodecyl-3-methylimidazolium chloride in step S2 of Example 9 with 1-butyl-3-methylimidazolium trifluoromethanesulfonylimide salt, otherwise the same as in Example 9.

[0299] Table 17 below shows the changes in current and reflectance difference in the visible and near-infrared range (380–2500 nm) for the colored and uncolored states of the devices prepared in Example 9 and Comparative Example 4. The testing method is the same as in Example 6. Table 17 shows that when using a rigid substrate with strong resistance to water and oxygen, adjusting the length of the carbon chain can also reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0300] Table 17

[0301] The coloring and fading times of devices prepared with ionic liquids of different chain lengths are shown in Table 18 below. The test method is the same as that in Example 6.

[0302] Table 18

[0303] Table 18 shows that when using a rigid substrate with strong resistance to water and oxygen, the coloring and fading times of ionic liquid devices with different chain lengths vary during cycling. The time of long-chain ionic liquids is more stable, which also reduces the difficulty of circuit control and packaging.

[0304] Example 10

[0305] 1.1 Mix 0.5g silver chloride, 5g 1-octyl-3-methylimidazolium chloride, 5g butyl acrylate, 0.5g polyethylene glycol diacrylate and 0.1g 2,4,6-trimethylbenzoyl diphenoxyphosphorus.

[0306] 1.2 Add 0.03g of spacers (the spacers are spherical in shape, made of polyacrylic acid resin, and have a particle size of 100μm) to the mixed solution and stir until homogeneous. Then, quickly coat the solution onto the surface of the PET-ITO-Au composite conductive film of the working electrode using a two-roller coating method to form an electrochromic layer with the same thickness as the spacer particle size (i.e., 100μm).

[0307] 1.3 The counter electrode silver mesh film and the coated PET-ITO-Au composite conductive film are combined and the slurry is cured by irradiation with ultraviolet light for 1 minute.

[0308] 1.4 Roller slicing, electrode attachment, and encapsulation yield a flexible photo-solid-state electrochromic device.

[0309] Example 11

[0310] A flexible photo-solid integrated electrochromic device was prepared according to the method of Example 10, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-dodecyl-3-methylimidazolium chloride.

[0311] Example 12

[0312] A flexible photo-solid integrated solid-state electrochromic device was prepared according to the method of Example 10, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-eicosyl-3-methylimidazolium chloride.

[0313] Example 13

[0314] A flexible photo-solid integrated electrochromic device was prepared according to the method of Example 10, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-benzyl-3-methylimidazolium chloride.

[0315] Example 14

[0316] A flexible photo-solid-state electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with lauryl acrylate.

[0317] Example 15

[0318] A flexible photo-solid-state electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with myristate acrylate.

[0319] Example 16

[0320] A flexible photo-solid integrated electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with eicosate acrylate, and the rest was the same as in Example 10.

[0321] Comparative Example 5

[0322] A flexible photo-solid-state electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with acrylic acid.

[0323] Comparative Example 6

[0324] A flexible photo-solid-state electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with vinylpyrrolidone.

[0325] Comparative Example 7

[0326] A flexible photo-solid-state electrochromic device was prepared according to the method of Example 10, except that butyl acrylate was replaced with acrylamide.

[0327] Comparative Example 8

[0328] A flexible photo-solid integrated electrochromic device was prepared according to the method of Example 10, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-ethyl-3-methylimidazolium chloride. However, a phase separation problem occurred during the mixing process. Since the hydrophobic acrylate monomers could not be miscible with the hydrophilic ionic liquid, a transparent and homogeneous electrochromic device could not be prepared.

[0329] Comparative Example 9

[0330] A flexible photo-solid integrated electrochromic device was prepared according to the method of Example 10, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-butyl-3-methylimidazolium chloride. However, phase separation occurred during the mixing process, making it impossible to fabricate a transparent and homogeneous electrochromic device.

[0331] The difference in current reflectance in the visible and infrared ranges (380–2500 nm) during cycling was monitored for the integrated electrochromic devices obtained in Examples 10–16 and Comparative Examples 5–7. The reflectance was measured according to the method in GB / T 33234-2016 "Test Method for Reflectance of Photothermal Power Generation Glass Mirrors". Under the conditions of an active area of ​​100 mm × 100 mm and an electrochromic layer thickness of 100 μm, the coloring time and fading time were determined as follows: the newly fabricated electrochromic devices were placed in an ultraviolet-visible spectrometer, and the average transmittance at 550 nm was recorded as the initial transmittance. The time taken for the transmittance to decrease by 65% ​​from the initial state after applying a coloring voltage (-0.6 V) was recorded as the coloring time t1, and the time taken for the transmittance to return to the initial state after applying a fading voltage (0.3 V) was recorded as the fading time t2. One cycle consists of the electrochromic device operating at a coloring voltage (-0.6V) for time t1, followed by an operation at a fading voltage (0.3V) for time t2. Transmittance tests are performed at 8 points on the edge and 1 point at the center during the cycle, as shown in Figure 2. An absolute change in the fading state at any of these 9 points exceeding 5% is considered an optical failure. The current cycle number is recorded as the test result, and the cycle test results are shown in Table 19.

[0332] Table 19 Cyclic Test Results of Electrochromic Devices

[0333] According to the test results in Table 19, the number of cycles in Example 10 was significantly higher than that in Comparative Examples 5-7. This result indicates that the hydrophilic, highly polar polymer is subject to accelerated device failure due to continuous erosion by moisture in the air. The integrated electrochromic device made of hydrophobic long-chain ionic liquid and hydrophobic acrylate polymer backbone has excellent water and oxygen resistance, which can effectively improve the device's cycle life.

[0334] The number of cycles in Examples 11 and 12 was the same as in Example 10, indicating that under the same polymer backbone, the hydrophobic ionic liquid had little impact on the device lifetime performance. The number of cycles in Example 13 was the same as in Example 10, indicating that devices prepared with long alkyl chains and phenyl groups, both being hydrophobic groups, exhibited similar lifetime performance. The number of cycles in Examples 14-16 was higher than that in Example 10. This result shows that acrylate monomers with longer alkyl chains further improved hydrophobicity, thus extending the device cycle life. The number of cycles in Example 16 was the same as in Examples 14 and 15, indicating that when the alkyl chain reaches a certain length, the improvement in hydrophobicity tends to plateau; therefore, the chain length of C20 has no difference in effect on device performance compared to the chain lengths of C14 and C12.

[0335] Simultaneously, the current magnitude of the device was recorded for each cycle number during the cyclic test. The current value was taken as the constant voltage method coloring value for 30 seconds at the corresponding cycle number. Under ambient temperature of 25℃ and humidity of 50%, a current change rate greater than 60% was considered an electrical failure, and the test was terminated. There was a difference between the current at different cycle numbers and the current in cycle 1. The current change rate was the ratio of this difference to the current in cycle 1. The current and current change rate during the cyclic process are shown in Table 20.

[0336] Table 20 Current and Current Change Rate during Cycling of Electrochromic Devices

[0337] In electrochromic layers, water content has a significant impact on the electrochemical window. Increased water content usually increases the conductivity and current density of the device, but it also disrupts the intermolecular forces at the device interface, reacts with electrodes to form oxides or corrosion products, and accelerates the aging of the device.

[0338] According to the test results in Table 20, the current change rate of Example 10 is much smaller than that of Comparative Examples 5-7. This result indicates that the integrated electrochromic device made of hydrophobic long-chain ionic liquid and hydrophobic acrylate polymer backbone can significantly reduce the impact of water vapor on electrochemical performance during cycling, improve device stability, and greatly extend the device's cycle life. This allows the integrated electrochromic device to possess excellent water and oxygen tolerance, effectively improving its cycle life.

[0339] The current change rate in Examples 14-16 was less than that in Examples 10, 11, 12 and 13. This result indicates that the more hydrophobic long alkyl chain acrylate monomers enhanced the water and oxygen tolerance of the device and further improved the cycle stability.

[0340] In the following embodiments, the device structure and fabrication method are as follows:

[0341] The working electrode uses a 10nm Au-ITO-PET metal film fabricated by magnetron sputtering, unless otherwise specified. The counter electrode uses a grooved PET film with organic silver paste. Flexible devices are fabricated using a coating-composite method, with the film thickness controlled by adding spacer particles (100μm) to the pre-curing formulation solution. Roll-to-roll coating is immediately followed by UV lamp (21mW / cm²). 2 The curing process was carried out, with the curing time varying depending on the slurry formulation, but all were ensured to be fully cured. After production, the films were cut into 10*10cm thin-film devices and then encapsulated using UV-curing adhesive. Finally, the gold film was placed face down on the glass and attached to it, with the gold film as the experimental observation surface. All processing was conducted at room temperature. In Comparative Example 14, electrode films were first attached to the glass, and then the glass was used to fabricate the device shell, which was bonded together with 100μm high-melting-point hot-melt pads to control the device spacing. Except for Example 24 and Comparative Example 17, for all examples and comparative examples, two 10cm*10cm devices were fabricated and experimental records were kept (referred to as A and B, respectively).

[0342] The testing method is as follows:

[0343] In room temperature air, a simple voltage-driven cycling method was used: voltage A for coloring for t1 seconds, voltage B for fading for t2 seconds. Voltage A was determined by the peak value of the reduction peak in the cyclic voltammetry curve of the gold film at the working electrode of each device tested by the electrochemical workstation (scan rate 10 mV / s), and voltage B was determined by the final plateau value of the oxidation peak in the same cyclic voltammetry curve. The difference in transmittance at 550 nm between the colored and transparent states was 25%. For example, as shown in Figure 3, the peak value in Figure 3 indicates that the coloring voltage A of the device is -0.28 V, and the fading voltage B is 0.16 V. One cycle of coloring and fading at this 25% change in transmittance at 550 nm constitutes one cycle. The number of cycles for each device was tested. When the device exhibited obvious optical failure, such as spots or patches of uncolored material, or when the transmittance change in one deposition process was less than 20%, or when electrochemical failure occurred, i.e., the device current remained below 10 during the coloring and fading process, the cycle was terminated. -5 A indicates the end of the cycle test, at which point the number of cycles represents the device's lifespan.

[0344] Example 17

[0345] The slurry formula is as follows:

[0346] Metal source: 712 mg silver chloride;

[0347] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 2732mg, polyethylene glycol diacrylate (PEGDA700) 68mg;

[0348] Initiator: (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide (TPO) 150 mg;

[0349] Additive: 6488 mg of (1-butyl-3-methylimidazole) chloride.

[0350] Comparative Example 10

[0351] The slurry formula is as follows:

[0352] Metal source: 712 mg silver chloride;

[0353] Polymerizable monomers: acrylic acid 2732mg, PEGDA700 68mg;

[0354] Initiator: TPO 150mg;

[0355] Additive: 6488 mg of (1-butyl-3-methylimidazole) chloride.

[0356] Comparative Example 11

[0357] The slurry formula is as follows:

[0358] Metal source: 712 mg silver chloride;

[0359] Polymerizable monomers: ethyl methacrylate 2732 mg, PEGDA700 68 mg;

[0360] Initiator: TPO 150mg;

[0361] Additive: 6488 mg of (1-butyl-3-methylimidazole) chloride.

[0362] Flexible devices were fabricated according to the above method and tested. The results are shown in Table 21.

[0363] Table 21

[0364] Test results show that the device prepared in Example 17 requires 60 seconds to cure, while Comparative Examples 10 and 11 require 300 seconds to cure.

[0365] Example 17 uses a polymeric ionic liquid framework with a relatively low oxygen content, resulting in minimal polymerization inhibition from oxygen. Furthermore, the device's driving energy is significantly reduced, but the fading time remains unchanged, while the cycle count increases significantly. In a hydrophilic electrolyte formulation, the device using the polymeric ionic liquid framework exhibits significantly improved cycle stability.

[0366] Example 18

[0367] The slurry formula is as follows:

[0368] Metal source: 712 mg silver chloride;

[0369] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 2732 mg, PEGDA700 68 mg;

[0370] Initiator: TPO 150mg;

[0371] Additives: 4320 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethanesulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0372] Comparative Example 12

[0373] The slurry formula is as follows:

[0374] Metal source: 712 mg silver chloride;

[0375] Polymerizable monomers: acrylic acid 2732mg, PEGDA700 68mg;

[0376] Initiator: TPO 150mg;

[0377] Additives: 4320 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethanesulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0378] Comparative Example 13

[0379] The slurry formula is as follows:

[0380] Metal source: 712 mg silver chloride;

[0381] Polymerizable monomers: ethyl methacrylate 2732 mg, PEGDA700 68 mg;

[0382] Initiator: TPO 150mg;

[0383] Additives: 4320 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethanesulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0384] Flexible devices were fabricated using the method described above and tested. The results are shown in Table 22.

[0385] Table 22

[0386] Test results show that the device prepared in Example 18 only requires 12 seconds to cure, while Comparative Examples 12 and 13 require 180 seconds to cure.

[0387] Example 18 uses a large amount of bis(trifluoromethane)sulfonamide (TFSI) anions in its additive, reducing the chloride ion concentration and allowing for a higher fading voltage of 0.5V. At this voltage, the gold film is not significantly electrochemically damaged, while the coloring voltage is further reduced to -0.34V without a significant impact on the coloring time. Furthermore, due to the low water-oxygen solubility of TFSI, its photocuring time in air is greatly shortened to 12 seconds. A comparison of Example 18 with Comparative Examples 12 and 13 demonstrates that even with changes to the anionic electrolyte or a change from hydrophilic to hydrophobic electrolyte, Example 18, by using a polymerizable monomer containing ionic groups, still exhibits superior electrodeposition reflectivity and room-temperature cycling stability compared to ordinary polymerizable monomers.

[0388] Example 19

[0389] The slurry formula is as follows:

[0390] Metal source: 712 mg silver chloride;

[0391] Polymerizable monomers: acrylic acid 2185.6 mg, N-vinylpyrrolidone 546.4 mg, PEGDA700 68 mg;

[0392] Initiator: TPO 150mg;

[0393] Additive: 6488 mg of (1-butyl-3-methylimidazole) chloride.

[0394] Example 20

[0395] The slurry formula is as follows:

[0396] Metal source: 712 mg silver chloride;

[0397] Polymerizable monomers: hydroxyethyl methacrylate 2185.6 mg, N-vinylpyrrolidone 546.4 mg, PEGDA700 68 mg;

[0398] Initiator: TPO 150mg

[0399] Additive: 6488 mg of (1-butyl-3-methylimidazole) chloride.

[0400] Comparative Example 14

[0401] The slurry formula is as follows:

[0402] Metal source: 712 mg silver chloride;

[0403] Polymerizable monomers: N / A;

[0404] Initiator: N / A;

[0405] Additives: 9220 mg of chlorinated (1-butyl-3-methylimidazolium) and 10 mg of polyvinylpyrrolidone (PVP24000).

[0406] Comparative Example 15

[0407] The slurry formula is as follows:

[0408] Metal source: 712 mg silver chloride;

[0409] Polymerizable monomers: acrylic acid 2732mg, PEGDA700 68mg;

[0410] Initiator: TPO 150mg;

[0411] Additives: 6488 mg of chlorinated (1-butyl-3-methylimidazole), 10 mg of PVP24000.

[0412] Comparative Example 16

[0413] The slurry formula is as follows:

[0414] Metal source: 712 mg silver chloride;

[0415] Polymerizable monomers: ethyl methacrylate 2732 mg, PEGDA700 68 mg;

[0416] Initiator: TPO 150mg;

[0417] Additives: 6488 mg of chlorinated (1-butyl-3-methylimidazole), 10 mg of PVP24000.

[0418] Flexible devices were fabricated according to the above method and tested. The results are shown in Table 23.

[0419] Table 23

[0420] Comparative Example 14 prepared a liquid device, while Examples 19, 20, 15, and 16 all prepared gel-type devices. In terms of cycle count, the liquid device had a significantly lower cycle count than the gel device. Comparative Examples 14, 15, and 16 revealed that the leveling agent PVP24000 only functions in solution systems, resulting in more uniform metal deposition and no significant dendrite growth. However, it does not function in gel devices, possibly because the leveling agent molecules are too large to diffuse rapidly and freely to the working electrode surface within the gel. However, in gel devices, adding polymerizable monomers with strong affinity for metal ions and coordinating functional groups not only inhibits dendrite growth across the entire surface, controlling dendrite formation to occur only at the device edges, but also significantly protects the silver mesh from electrochemical corrosion, greatly increasing the cycle count.

[0421] Dendritic growth is observed on the working electrode; full-surface dendritic growth is shown in Figure 4, while the absence of dendritic growth is shown in Figure 5. Images of the silver mesh on the organic silver paste film of the counter electrode show complete solid lines in Figure 6, while damaged, broken lines are shown in Figure 7.

[0422] Example 21

[0423] The slurry formula is as follows:

[0424] Metal source: 712 mg silver chloride;

[0425] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 2185.6 mg, N-vinylpyrrolidone 546.4 mg, PEGDA700 68 mg;

[0426] Initiator: TPO 150mg;

[0427] Additives: 4320 mg of 1-n-butyl-1-methylimidazolium di(trifluoromethylsulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0428] Example 22

[0429] The slurry formula is as follows:

[0430] Metal source: 712 mg silver chloride;

[0431] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 2185.6 mg, vinyltris(2-methoxyethoxy)silane 546.4 mg, PEGDA700 68 mg;

[0432] Initiator: TPO 150mg;

[0433] Additives: 4320 mg of 1-n-butyl-1-methylimidazolium di(trifluoromethylsulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0434] Example 23

[0435] The slurry formula is as follows:

[0436] Metal source: 712 mg silver chloride;

[0437] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 2185.6 mg, N,N'-methylenebisacrylamide 546.4 mg, PEGDA700 68 mg;

[0438] Initiator: TPO 150mg;

[0439] Additives: 4320 mg of 1-n-butyl-1-methylimidazolium di(trifluoromethylsulfonyl)imide, 2168 mg of (1-butyl-3-methylimidazolium chloride).

[0440] Flexible devices were fabricated using the method described above and tested. The results are shown in Table 24.

[0441] Table 24

[0442] Examples 21, 22, and 23 achieved a dual positive gain effect by simultaneously adding polymerizable monomers containing ionic liquid groups and polymerizable monomers coordinated with metal ions. This reduced the driving voltage, thereby lowering the operating current of the device. The polymeric cationic framework provided an electrostatic shielding effect, unifying the silver ion flux on the working electrode surface and promoting uniform silver deposition. Furthermore, the large number of functional groups on the polymer molecules with strong affinity for silver ions suppressed and balanced the electroplating rate, thus preventing dendritic deposition and growth. The silver mesh remained intact and solid, protecting the complete solid state of the silver mesh and achieving a long life cycle of over 8000 cycles.

[0443] Example 24

[0444] The slurry formula is as follows:

[0445] Metal source: 904 mg silver chloride;

[0446] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 4708mg, N,N'-methylenebisacrylamide 844mg, vinyltris(2-methoxyethoxy)silane 300mg, PEGDA700 148mg;

[0447] Initiator: TPO 150mg;

[0448] Additives: 10124 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethylsulfonyl)imide, 2972 ​​mg of (1-butyl-3-methylimidazolium chloride).

[0449] Comparative Example 17

[0450] The slurry formula is as follows:

[0451] Metal source: 904 mg silver chloride;

[0452] Polymerizable monomers: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt 5852mg, PEGDA700 148mg;

[0453] Initiator: TPO 150mg;

[0454] Additives: 10124 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethylsulfonyl)imide, 2972 ​​mg of (1-butyl-3-methylimidazolium chloride).

[0455] Comparative Example 18

[0456] The slurry formula is as follows:

[0457] Metal source: 904 mg silver chloride;

[0458] Polymerizable monomers: acrylic acid 4708mg, N,N'-methylenebisacrylamide 844mg, vinyltris(2-methoxyethoxy)silane 300mg, PEGDA700 148mg;

[0459] Initiator: TPO 150mg;

[0460] Additives: 10124 mg of 1-n-butyl-1-methylpyrrolidine di(trifluoromethylsulfonyl)imide, 2972 ​​mg of (1-butyl-3-methylimidazolium chloride).

[0461] Flexible devices were fabricated using the method described above and tested. The results are shown in Table 25.

[0462] Table 25

[0463] The device of Example 24B exhibits a visible light transmittance of 65% in the faded state, as shown in Figure 8, and a coloring state with a coloring level of 5%, as shown in Figure 9. Thanks to the electrostatic shielding effect provided by the polymeric cationic framework, the silver ion flux is uniformly concentrated on the working electrode surface, promoting uniform silver deposition. Examples 24A, 24B, and Comparative Examples 17A, 17B all show uniform color change. In Comparative Examples 18A and 18B, when the coloring level drops below 30%, the coloring becomes more pronounced near the working electrode and slower at the distal end. This demonstrates that adding polymerizable monomers containing polymerizable monomers that can coordinate with metal ion polymers and polymerizable monomers with ionic liquid groups can achieve uniform color change in large-area devices. Furthermore, due to the use of a polymeric ionic liquid framework with TFSI anions and an electrolyte containing a large number of TFSI anions, Example 24 can undergo fading at -20°C or 100°C, exhibiting a wide operating temperature range. Moreover, Example 24 maintains essentially unchanged color transmittance in open-circuit mode at room temperature for over 7 days after coloring.

[0464] The fading spectrum of the device in Example 24B is shown in Figure 10.

[0465] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

A reflective integrated electrochromic device, comprising, in sequence: First substrate layer, working electrode layer, integrated electrochromic layer, counter electrode layer and second substrate layer; The integrated electrochromic layer includes a metal source compound; The metal source compound is selected from one or more of the following: silver chloride, silver acetate, silver nitrate, silver perchlorate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, silver bis(trifluoromethanesulfonyl)imide, copper fluoride, copper chloride, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, gold chloride, gold sulfide, nickel chloride, nickel sulfate, cobalt chloride, or platinum chloride. The reflective integrated electrochromic device according to claim 1 is characterized in that, The metal source compound is selected from silver chloride, silver hexafluorophosphate, silver tetrafluoroborate, or silver bis(trifluoromethanesulfonyl)imide. The mass fraction of the metal source compound in the integrated electrochromic layer is 1% to 30%. The reflective integrated electrochromic device according to claim 1 is characterized in that, The integrated electrochromic layer also includes an ionic liquid; The ionic liquid is selected from one or more of the following: alkyl imidazolium salts, alkyl pyridine salts, alkyl pyrrole salts, alkyl quaternary ammonium salts, alkyl quaternary phosphine salts, fluoroalkyl imidazolium salts, fluoroalkyl pyridine salts, fluoroalkyl pyrrole salts, fluoroalkyl quaternary ammonium salts, and fluoroalkyl quaternary phosphine salts. The reflective integrated electrochromic device according to claim 3 is characterized in that, The ionic liquid has 6 or more carbon atoms. The reflective integrated electrochromic device according to claim 4 is characterized in that, The ionic liquid has 6 to 20 carbon atoms. The reflective integrated electrochromic device according to claim 5 is characterized in that, The ionic liquid is selected from one or more of 1-C6-C20 alkyl-3-methylimidazolium salts, 1-vinyl-3-C6-C20 alkylimidazolium salts, and N-C6-C20 alkylpyridinium salts; The anions of the above ionic liquids are selected from halide ions, tetrafluoroborate ions, hexafluorophosphate ions, fluorosulfonyl imide ions, trifluoromethanesulfonyl imide ions, or bis(trifluoromethanesulfonyl imide) ions. The reflective integrated electrochromic device according to claim 3 is characterized in that, The ionic liquid has a mass content of 20% to 90% in the integrated electrochromic layer. The reflective integrated electrochromic device according to claim 1 is characterized in that, The integrated electrochromic layer also includes a polymer compound; The polymer compound is generated by an integrated polymerization reaction of one or more of the following within the device: a monomer, an initiator, a crosslinking agent, a catalyst, and a polymerization inhibitor. The reflective integrated electrochromic device according to claim 8 is characterized in that, The polymerizable monomers include one or more of the following: acrylic acid and its derivatives, acrylates and their derivatives, hydroxyethyl acrylate and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, diphenylmethane diisocyanate and its derivatives, toluene diisocyanate and its derivatives, isophorone diisocyanate and its derivatives, dicyclohexylmethane diisocyanate and its derivatives, hexamethylene diisocyanate and its derivatives, L-lysine diisocyanate and its derivatives, polyols and their derivatives, polyamines and their derivatives, phenyl dioxide epoxy resin and its derivatives, glycidyl ether and its derivatives; The crosslinking agent includes one or more of the following: ethylene glycol dimethacrylate and its derivatives, polyethylene glycol dimethacrylate and its derivatives, polydipentaerythritol pentaacrylate and its derivatives, ethoxylated trimethylolpropane triacrylate and its derivatives, N,N'-methylenebisacrylamide and its derivatives. The reflective integrated electrochromic device according to claim 9 is characterized in that, The polymer monomers include hydrophobic polymer monomers of acrylates. The reflective integrated electrochromic device according to claim 10 is characterized in that, The acrylate hydrophobic polymer monomers include one or more of the following: methyl acrylate and its derivatives, methyl methacrylate and its derivatives, ethyl acrylate and its derivatives, ethyl methacrylate and its derivatives, propyl acrylate and its derivatives, propyl methacrylate and its derivatives, butyl acrylate and its derivatives, butyl methacrylate and its derivatives, n-pentyl acrylate and its derivatives, isoamyl acrylate and its derivatives, hexyl acrylate and its derivatives, hexyl methacrylate and its derivatives, n-octyl acrylate and its derivatives, n-octyl methacrylate and its derivatives, isooctyl acrylate and its derivatives, isooctyl methacrylate and its derivatives, lauryl acrylate and its derivatives, lauryl methacrylate and its derivatives, myristyl acrylate and its derivatives, myristyl methacrylate and its derivatives, cyclohexyl methacrylate and its derivatives, isobornyl acrylate and its derivatives, isobornyl methacrylate and its derivatives, styrene and its derivatives, dicyclopentenyl acrylate and its derivatives, benzyl acrylate and its derivatives, and benzyl methacrylate and its derivatives. The reflective integrated electrochromic device according to claim 10 is characterized in that, The polymerizing monomer further includes a comonomer; the comonomer includes one or more of acrylic monomers, acrylamide monomers, acrylate monomers, and olefin derivatives; And / or, the polymeric monomer may further include a crosslinking agent. The reflective integrated electrochromic device according to claim 12 is characterized in that, The comonomers include one or more of the following: acrylic acid, butylated acrylate, cinnamic acid, methyl acrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, glycidyl methacrylate, vinyl acetate, N-vinyl-2-imidazolium and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, acrylamide, 2-acryloylamino-2-methylpropanesulfonic acid, 2-acryloylamino-dodecyl sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, m-phenoxybenzyl methacrylate, 2-phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, propoxyl nonylphenol acrylate, and dicyclopentyl methacrylate. And / or, the crosslinking agent comprises one or more of the following: tricyclodecanediethanol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol dimethacrylate, bisphenol A diacrylate ethoxylate, tricyclodecanediethanol dimethacrylate, 1,12-dodecyl dimethacrylate, N,N-methylenebisacrylamide, and 2-hydroxyethyl methacrylate phosphate. The reflective integrated electrochromic device according to claim 8 or 10 is characterized in that, The integrated electrochromic layer also includes an ionic liquid; The molecular structure of ionic liquids contains hydrophobic long alkyl and / or aryl functional groups. The reflective integrated electrochromic device according to claim 14 is characterized in that, The mass of the ionic liquid is 5% to 50% of the mass of the integrated electrochromic layer; And / or, the ionic liquid includes one or more of the following: imidazole salt ionic liquids, pyridine salt ionic liquids, pyrrole salt ionic liquids, quaternary ammonium salt ionic liquids, quaternary phosphine salt ionic liquids, fluoroimidazolium salt ionic liquids, fluoropyridine salt ionic liquids, fluoropyrrole salt ionic liquids, fluoroquaternary ammonium salt ionic liquids, and fluoroquaternary phosphine salt ionic liquids. The reflective integrated electrochromic device according to claim 14 is characterized in that, The ionic liquid is selected from 1-octyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium tetrafluoroborate, 1-dodecyl-3-methylimidazolium hexafluorophosphate, 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium tetrafluoroborate, 1-dodecyl-3-methylimidazolium hexafluorophosphate, 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. The imine salt, 1-tetradecyl-3-methylimidazolium tetrafluoroborate, 1-tetradecyl-3-methylimidazolium hexafluorophosphate, 1-tetradecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine salt, 1-hexadecyl-3-methylimidazolium tetrafluoroborate, 1-hexadecyl-3-methylimidazolium hexafluorophosphate, 1-hexadecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine salt, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine salt, or one or more of the following: The reflective integrated electrochromic device according to any one of claims 1 to 16 is characterized in that, The integrated electrochromic layer also includes one or more of solvents and additives; The solvent includes one or more of the following: γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methylpyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, sulfolane and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives. And / or, the additives include one or more of the following: silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents, rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers, hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, and silica microspheres; And / or, the additives include one or more of coupling agents, antioxidants, light stabilizers, thickeners, electrolyte supplements, and spacers; And / or, the additives include one or more of initiators, coupling agents, surfactants, thickeners, and spacers; The initiator includes one or more of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, benzaldehyde-formaldehyde trimer, acryloylcarboxylate diester, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoyl phosphate ethyl ester, 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, lithium phenyl(2,4,6-trimethylbenzoyl)phosphate, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 1-hydroxyphenylcyclohexanone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropanone; And / or, the coupling agent includes silane coupling agents and / or phthalate coupling agents; And / or, the surfactant includes one or more of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants; And / or, the thickener includes one or more of acrylate polyols, sodium polyacrylate, sodium polypentaerythritol acrylate, sodium alginate, and carboxymethyl cellulose; And / or, the spacers include one or more of polystyrene microspheres, polyacrylate microspheres, and silica microspheres. The reflective integrated electrochromic device according to claim 1 is characterized in that, The conductive layer material of the working electrode is selected from one or more of the following: indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, metallic copper, metallic silver, metallic aluminum, metallic gold, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, indium tin oxide-gold multilayer composite material, graphene, and carbon nanotubes to make a mesh or planar transparent conductive film. The reflective integrated electrochromic device according to claim 1 is characterized in that, The conductive layer material of the counter electrode is selected from transparent metal conductive electrodes; The transparent conductive metal electrode is selected from one or more of the following: mesh or film made of copper nanowires, silver nanowires, aluminum nanowires, copper mesh, silver mesh, aluminum mesh, indium tin oxide-copper multilayer composite film or mesh, indium tin oxide-silver multilayer composite film or mesh, and indium tin oxide-aluminum multilayer composite film or mesh. The reflective integrated electrochromic device according to claim 19 is characterized in that, The transparent conductive metal electrode is selected from one or more of the following: a silver mesh, a mesh or film made of silver nanowires, an indium tin oxide-silver multilayer composite film or mesh. The reflective integrated electrochromic device according to claim 1 is characterized in that, The first substrate layer and the second substrate layer are independently selected from inorganic substrates, organic substrates or inorganic-organic composite substrates. The reflective integrated electrochromic device according to claim 1 is characterized in that, The thickness of the integrated electrochromic layer is 5–3000 μm. The reflective integrated electrochromic device according to claim 8 is characterized in that, The polymeric monomers include polymeric monomers having ionic liquid groups and / or polymeric monomers that can coordinate with metal ions. The crosslinking agent includes one or more of polyethylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. The reflective integrated electrochromic device according to claim 23 is characterized in that, The polymeric monomer structure having ionic liquid groups includes: polymeric groups, organic cations, and inorganic or organic anions; The polymeric groups include one or more of the following: olefinic, alkynic, and epoxy groups; The organic cations include one or more of the following: quaternary ammonium salt ions, quaternary phosphorus salt ions, imidazole salt ions, pyrrole salt ions, pyridinium salt ions, piperidine salt ions, morpholine salt ions, thiophene salt ions, carbazole salt ions, and guanidine salts; The inorganic or organic anions include one or more of the following anions: Halogen ions, alkali salt ions, fluorine-containing anions, oxyacid anions, amino acid anions, ester anions, cyanide-containing anions, and halide metal salt anions; The halide ions are selected from chloride ions, bromide ions, iodide ions, or bromide trine ions; The alkaline salt ions are selected from hydroxide ions, carbonate ions, bicarbonate ions, bisulfate ions, phosphate ions, or hydrogen phosphate ions. The fluorine-containing anion is selected from tetrafluoroborate ion, hexafluorophosphate ion, bis(fluorosulfonyl)imide ion, bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonate ion, trifluoromethanesulfonylimide ion, antimony hexafluoride ion, or trifluoroacetate ion. The anion of the oxyacid is selected from sulfate ion, nitrate ion, perchlorate ion, acetate ion, methanesulfonate ion, p-toluenesulfonate ion, oleate ion, ibuprofen salt ion or geraniate ion. The amino acid anions are selected from lactate ions, cysteine ​​ions, or glycine ions; The ester anion is selected from hydrosulfide ion, dimethyl phosphate salt ion, dibutyl phosphate salt ion, methyl sulfate salt ion, ethyl sulfate salt ion or polyacrylamide anion; The cyano-containing anion is selected from dicyandiamide salt ions or thiocyanate; The halide metal salt anions are selected from ferric chloride anion, aluminum chloride anion, titanium chloride anion, zinc chloride anion, or copper chloride anion. The reflective integrated electrochromic device according to claim 24 is characterized in that, The polymeric monomer having an ionic liquid group is selected from 1-vinyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinyl-3-methylimidazolium sulfate methyl ester, 1-vinyl-3-methylimidazolium iodide, 1-vinyl-3-methylimidazolium bromide, 1-vinyl-3-methylimidazolium chloride, 1-vinyl-3-methylimidazolium dimethyl phosphate, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-methylimidazolium hexafluoroantimonate, 1-vinyl-3-methylimidazolium trifluoromethanesulfonate, 1-vinyl-3-methylimidazolium perchlorate, 1-vinyl-3-methylimidazolium nitrate, 1-vinyl-3-methylimidazolium methanesulfonate, 1-vinyl-3-methylimidazolium nitrate, 1-vinyl-3-methylimidazolium methanesulfonate, 1-vinyl-3-methylimidazolium... 1-Ethyl-3-vinylimidazolium p-toluenesulfonate, 1-vinyl-3-vinylimidazolium acetate, 1-ethyl-3-vinylimidazolium bromide, 1-ethyl-3-vinylimidazolium iodide, 1-ethyl-3-vinylimidazolium ethyl sulfate, 1-ethyl-3-vinylimidazolium diethyl phosphate, 1-ethyl-3-vinylimidazolium tetrafluoroborate, 1-ethyl-3-vinylimidazolium hexafluorophosphate, 1-ethyl-3-vinylimidazolium hexafluoroantimonate, 1-ethyl-3-vinylimidazolium nitrate, 1-ethyl-3-vinylimidazolium trifluoromethanesulfonate, 1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-vinylimidazolium perchlorate, 1-ethyl-3-vinylimidazolium thiocyanate, 1-ethyl-3-vinylimidazolium... Alkenylimidazolium methanesulfonate, 1-Ethyl-3-vinylimidazolium p-toluenesulfonate, 1-Ethyl-3-vinylimidazolium acetate, 1-Ethyl-3-vinylimidazolium trifluoroacetate, 1-Ethyl-3-vinylimidazolium hydrogen sulfate, 1-propyl-3-vinylimidazolium bromide, 1-propyl-3-vinylimidazolium iodide, 1-propyl-3-vinylimidazolium hexafluorophosphate, 1-propyl-3-vinylimidazolium hexafluoroantimonate, 1-propyl-3-vinylimidazolium nitrate, 1-propyl-3-vinylimidazolium trifluoromethanesulfonate, 1-propyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-propyl-3-vinylimidazolium perchlorate, 1-propyl-3-vinylimidazolium thiocyanate, 1-propyl-3-vinylimidazolium methanesulfonate Salts, 1-propyl-3-vinylimidazolium p-toluenesulfonate, 1-propyl-3-vinylimidazolium acetate, 1-propyl-3-vinylimidazolium trifluoroacetate, 1-butyl-3-vinylimidazolium chloride, 1-butyl-3-vinylimidazolium bromide, 1-butyl-3-vinylimidazolium tetrafluoroborate, 1-butyl-3-vinylimidazolium hexafluorophosphate, 1-butyl-3-vinylimidazolium trifluoromethanesulfonate, 1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-vinylimidazolium hydrogen sulfate, 1-butyl-3-vinylimidazolium methanesulfonate, 1-butyl-3-vinylimidazolium dibutyl phosphate, 1-butyl-3-vinylimidazolium dicyandiamide, 1-butyl-3-vinylimidazolium hexafluoroantimonate1-Butyl-3-vinylimidazolium nitrate, 1-Butyl-3-vinylimidazolium octylsulfonate, 1-Butyl-3-vinylimidazolium thiocyanate, 1-Butyl-3-vinylimidazolium p-toluenesulfonate, 1-benzyl-3-vinylimidazolium bromide, 1-benzyl-3-vinylimidazolium chloride, 1-benzyl-3-vinylimidazolium hexafluorophosphate, 1-benzyl-3-vinylimidazolium hexafluoroantimonate, 1-benzyl-3-vinylimidazolium tetrafluoroborate, 1-benzyl-3-vinylimidazolium methanesulfonate, 1-benzyl-3-vinylimidazolium trifluoromethanesulfonate, 1-benzyl-3-vinylimidazolium bis(trifluoromethanesulfonate) One or more of the following: 1-benzyl-3-vinylimidazolium hydrogen sulfate, 1-benzyl-3-vinylimidazolium nitrate, 1-benzyl-3-vinylimidazolium methanesulfonate, 1-benzyl-3-vinylimidazolium dicyandiamide, 1-benzyl-3-vinylimidazolium thiocyanate, 1-allyl-3-vinylimidazolium chloride, 1-allyl-3-vinylimidazolium bromide, 1-allyl-3-vinylimidazolium iodide, 1-allyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-vinylimidazolium hexafluorophosphate, and 1-allyl-3-vinylimidazolium tetrafluoroborate; The polymeric monomers having ionic liquid groups constitute 5% to 70% of the mass content of the integrated electrochromic layer. The reflective integrated electrochromic device according to claim 23 is characterized in that, The polymerizable monomer that can coordinate with metal ions is selected from one or more of N-vinylpyrrolidone, vinyltris(2-methoxyethoxy)silane, N,N'-methylenebisacrylamide, acrylamide, dimethoxydivinylsilane, dimethyl(dimethylamino)vinylsilane, triethoxy(1-phenylvinyl)silane, methylvinyldimethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate. The polymeric monomers that can coordinate with metal ions have a mass content of 1% to 48% in the integrated electrochromic layer. The reflective integrated electrochromic device according to claim 23 is characterized in that, The polymeric monomer includes: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt; Or may include: acrylic acid and N-vinylpyrrolidone; Or may include: hydroxyethyl methacrylate and N-vinylpyrrolidone; Or may include: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and N-vinylpyrrolidone; Or may include: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and vinyltris(2-methoxyethoxy)silane; Or may include: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt and N,N'-methylenebisacrylamide; Or include: 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, N,N'-methylenebisacrylamide and vinyltris(2-methoxyethoxy)silane. The reflective integrated electrochromic device according to claim 23 is characterized in that, The integrated electrochromic layer also includes additives; The additives include one or more of diluents, leveling agents, and initiators; The diluent includes 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-butyl-3-methylimidazolium chloride), 1-n-butyl-1-methylpyrrolidine di(trifluoromethanesulfonyl)imide, 1-n-butyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide, (1-ethyl-3-methylimidazolium chloride), (1-butyl-3-methylimidazolium bromide), (1-ethyl-3-methylimidazolium bromide), and (1-butyl-2,3-methylimidazolium chloride). 1,2-Dimethyl-3-hydroxyethylimidazolium (DIMM), 1,2-Dimethyl-3-hydroxyethylimidazolium p-toluenesulfonate, 1,2-Dimethyl-3-hydroxyethylimidazolium bis(trifluoromethanesulfonylimide), 1-Ethyl-3-methylimidazolium hexafluorophosphate, 1-Ethyl-3-methylimidazolium tetrafluoroborate, trimethylhydroxyethylamine bis(trifluoromethanesulfonyl)imide, N-octylpyridine hydrogen sulfate, N-octylpyridine perchlorate, N-hexylpyridine bromide, trimethylhydroxyethylamine chloride, bromide N-Methylethylpiperidine, N-methylbutylpiperidine bis(trifluoromethanesulfonyl)imide salt, (N-methylbutylpyrrolidine) chloride, (N-methylbutylpyrrolidine) bromide, N-methylethylmethanesulfonate, methylethylmorpholine bromide, N-methylpropylmorpholine bis(trifluoromethanesulfonyl)imide salt, methyltributylphosphine tetrafluoroborate, methyltributylphosphine hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-epoxypropyl-3-methylimidazolium) chloride The following are one or more of the following: 1-epoxypropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-carboxymethyl-3-methylimidazolium chloride), N-sulfonic acid butyl-3-methylimidazolium hydrogen sulfate, (1-acetonitrile-3-methylimidazolium chloride), 1-butyl-3-methylimidazolium hydroxide, 1-(propyltriethoxy)-3-methylimidazolium chloride, dimethyl sulfoxide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, and dioctyl phthalate; The leveling agent includes one or more of the following: polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, N,N-diethylpropynylamine sulfate, polyacrylic acid, polystyrene, poly(sodium 4-styrene sulfonate and maleic acid) copolymer, copolymer of 1-vinylimidazolium and 1,4-butanediol glycidyl ether, and fatty acid quaternary ammonium salts. The initiator is selected from thermal initiators or photoinitiators; The thermal initiator includes one or more of azobisisobutyronitrile, benzoyl peroxide, persulfate, di-tert-butyl peroxide, benzoyl peroxide, and thiobenzoyl. The photoinitiators include photoinitiator 2959, TPO, photoinitiator 184, TPO-L, photoinitiator 1173, photoinitiator 907, photoinitiator 369, photoinitiator 1490, photoinitiator 1700, diazonium salts, diaryliodomonium salts, triarylthionium salts, alkylthionium salts, iron aromatic salts, sulfonyloxyketones, triarylsiloxane ethers, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin... One or more of the following: eugenol, diphenyl ethyl ketone, α,α-dimethoxy-α-phenyl acetophenone, α,α-diethoxyacetophenone, α-hydroxyalkyl acetophenone, α-aminealkyl acetophenone, aromatic phosphine oxide, bisbenzoylphenylphosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, michidone, thiopropoxythioxanthrone, isopropylthioxanthrone, fluorinated diphenyltitanium, bis(pentafluorophenyl)titanium, and photoinitiator LAP. The method for preparing the reflective integrated electrochromic device according to any one of claims 1 to 28 includes the following steps: S1) Apply the integrated electrochromic layer solution or slurry to the surface of the counter electrode or working electrode, seal the film and solidify the solution or slurry; S2) Laser slicing, electrode attachment, and encapsulation yield a reflective integrated electrochromic device; Or it may include the following steps: S11) Drill pre-drilled holes on a rigid conductive substrate, attach the working electrode plate and the counter electrode plate face to face, and use spacers to control the plate spacing to form a hollow device shell. S22) Inject the integrated electrochromic layer solution or slurry into the hollow device shell through the aforementioned pre-formed holes; S33) Dispensing and sealing to solidify the solution or slurry, resulting in a reflective integrated electrochromic device.

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