Solvent-free acrylate system electro-reflective device and preparation method thereof

Abstract

The invention provides a solvent-free acrylate system electro-reflective device. The solvent-free acrylate system electro-reflective device comprises an electro-reflective layer, the electro-reflective layer is formed by curing electro-reflective slurry; the electro-reflective slurry comprises a metal silver compound component, a polymerizable monomer and an additive, the polymerizable monomer comprises an acrylic ester hydrophobic polymer monomer. Compared with the prior art, a solvent-free acrylate system is adopted, acrylate molecules with hydrophobic groups are used as a high-molecular main body framework, so that the integrated electro-reflective layer is made into a hydrophobic layer, the overall water-oxygen endurance capacity is effectively improved, the cycling stability of a device can be greatly improved, and the service life of the device can be greatly prolonged; and meanwhile, the acrylate gel is high in strength and strong in adhesive strength, can be used for preparing flexible roll-to-roll process, widens the application field and is convenient for industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electrochromic light reflection, and particularly relates to a solvent-free acrylate system electrochromic light reflection device and a preparation method thereof. BACKGROUND

[0002] The electrochromic device generally refers to that the optical properties such as reflectivity, transmittance and absorptivity of a material are changed stably and reversibly by applying an external electric field, so as to actively and dynamically control the light and solar radiation heat. The traditional absorption type electrochromic device can change the transmittance by applying an external electric field, but the reflectivity changes little. The new generation of electrochromic light reflection technology is that the metal cations in the active layer are reduced on the color changing electrode plate under the action of an external electric field to form a dense metal film. Based on the characteristics of the metal itself, the metal film can reflect all or part of the visible light, infrared and other bands back, has a large transmittance and reflectivity control window, and is an active light and heat management control technology.

[0003] At present, the absorption type electrochromic device is on sale in the market, and the reflective type is still in the research stage. The most studied is the reversible silver deposition system. However, the existing reversible silver electrodeposition system has great limitations when applied to integrated devices: one kind is that the dissolution of silver salt requires a strong polar environment, and various polar components are dissolved by adding solvents. However, this method has the problem of solvent evaporation, and the device cannot work stably for a long time. Another kind is a hydrophilic system formed by the mutual solubility of strong polar electrolyte and strong polar polymer. Although this system does not have the problem of solvent evaporation, it still has the characteristics of slow water absorption. Under the influence of external water and oxygen, the current control is unstable, and the cycle life is easily attenuated.

[0004] The document "Dynamic glazing with switchable solar reflectance for radiative cooling and solar heating" shows a dual-mode glass panel by reversibly electrodeposited silver film on transparent glass, which has switchable reflectivity. The electrolyte is prepared by dissolving tetrabutylammonium bromide (TBABr), silver nitrate (AgNO3), copper chloride (CuCl2) and polyvinyl butyral (PVB) into dimethyl sulfoxide (DMSO), and the electrolyte is sealed by a transparent silicone rubber with a thickness of 0.5 mm. The document uses electrochromic light reflection technology, but the electrolyte contains the solvent dimethyl sulfoxide, and the solvent system has poor stability due to its volatility.

[0005] The document "Bistable Variable Infrared Emissivity Device Based on Reversible Silver Electrodeposition" mentions that the electrolyte layer composition includes silver bromide (AgBr), ionic liquid, polyvinyl butyral (PVB) and dimethyl sulfoxide (DMSO), but the electrolyte system also has a solvent dimethyl sulfoxide.

[0006] The document "Silver Electrodeposition from Room Temperature Ionic Liquid Electrolytes" reports a room temperature ionic liquid liquid formula, which uses 1-butyl-1-methylpyridine bis(trifluoromethyl sulfonyl) imine, 1-butyl-2, 3-dimethyl imidazole bis(trifluoromethyl sulfonyl) imine and metal silver source, but it is also reported that the ionic liquid has high sensitivity to water (including atmospheric humidity), which reduces the cycle stability, and the electrochromic device is very sensitive to external water and oxygen, the invasion of water and oxygen will cause the electrode surface or active layer to fail, which seriously reduces the performance and service life of the device. SUMMARY

[0007] Therefore, the technical problem to be solved by the present application is to provide a solvent-free acrylate system electrochromic device with high water and oxygen resistance and a preparation method thereof.

[0008] The present application provides a solvent-free acrylate system electrochromic device, comprising an electrochromic layer; the electrochromic layer is formed by curing an electrochromic slurry; the electrochromic slurry comprises a metal silver compound component, a polymerizable monomer and an additive.

[0009] The polymerizable monomer comprises an acrylate hydrophobic polymer monomer.

[0010] Preferably, the additive comprises an ionic liquid; the molecular structure of the ionic liquid comprises a hydrophobic long alkyl and / or aryl functional group.

[0011] Preferably, the mass of the ionic liquid is 5% to 50% of the mass of the electrochromic slurry.

[0012] And / or, the ionic liquid comprises one or more of imidazole salt ionic liquid, pyridine salt ionic liquid, pyrrole salt ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, fluorinated imidazole salt ionic liquid, fluorinated pyridine salt ionic liquid, fluorinated pyrrole salt ionic liquid, fluorinated quaternary ammonium salt ionic liquid and fluorinated quaternary phosphonium salt ionic liquid.

[0013] Preferably, the mass of the metal silver compound component is 1% to 30% of the mass of the electrochromic reflective paste;

[0014] Preferably, the mass of the metal silver compound component is 1% to 30% of the mass of the electrochromic reflective paste;

[0015] Preferably, the mass of the metal silver compound component is 1% to 30% of the mass of the electrochromic reflective paste.

[0016] Preferably, the metal silver compound component is 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, and silver bistrifluoromethanesulfonimide;

[0017] Preferably, the mass of the metal silver compound component is 1% to 30% of the mass of the electrochromic reflective paste;

[0018] and / or, the ionic liquid is selected from one or more of 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-tetradecyl-3-methylimidazolium tetrafluoroborate, 1-tetradecyl-3- methylimidazolium hexafluorophosphate, 1-tetradecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexadecyl-3-methylimidazolium tetrafluoroborate, 1-hexadecyl-3-methylimidazolium hexafluorophosphate, 1- hexadecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-benzyl-3- methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

[0019] Preferably, the polymerizable monomer further comprises a co-monomer; the co- monomer comprises one or more of an acrylic monomer, an acrylamide monomer, an acrylate monomer, and an olefin derivative;

[0020] and / or, the polymerizable monomer further comprises a cross-linking agent;

[0021] and / or, the additive further comprises one or more of an initiator, a cross-linking agent, a coupling agent, a surfactant, a thickening agent, and a spacer.

[0022] Preferably, the co-monomer comprises one or more of acrylic acid, fumaric acid, 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-imidazole and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamidododecylsulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, p- phenoxybenzyl acrylate, 2-phenoxyethyl acrylate, o-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, propoxylated nonylphenol acrylate, and bicyclopentanymethyl acrylate.

[0023] and / or, the crosslinking agent comprises one or more of tricyclodecane dimethanol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, tricyclodecane dimethanol dimethacrylate, 1,12-dodecanediol dimethacrylate, N,N-methylenebisacrylamide and 2-hydroxyethyl methacrylate phosphate ester;

[0024] and / or, the initiator comprises one or more of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, dibenzoyl peroxide, benzaldehyde-formaldehyde trimer, acryloyl carboxylic acid diester, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoyl ethyl phosphonate, 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, phenyl(2,4,6-trimethylbenzoyl)phosphonium lithium salt, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 1-hydroxyphenyl cyclohexanone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether and 2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiophenone;

[0025] and / or, the coupling agent comprises a silane coupling agent and / or a phthalate coupling agent;

[0026] and / or, the surfactant comprises one or more of a cationic surfactant, an anionic surfactant, a non-ionic surfactant, a zwitterionic surfactant;

[0027] and / or, the thickening agent comprises one or more of an acrylate polyol, sodium polyacrylate, sodium poly-pentaerythritol acrylate, sodium alginate and carboxymethyl cellulose;

[0028] and / or, the spacer comprises one or more of polystyrene microspheres, polyacrylate microspheres and silica microspheres.

[0029] Preferably, the first substrate layer, the working electrode layer, the electrochromic layer, the counter electrode layer and the second substrate layer are sequentially arranged.

[0030] Preferably, 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.

[0031] The inorganic substrate layer is selected from one or more of glass, diamond and ceramic;

[0032] The organic base layer includes one or more of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, perfluoroethylene propylene, ethylene-vinyl acetate copolymer, polyimide, thermoplastic polyurethane, and polysulfone-acrylonitrile-butadiene-styrene terpolymer.

[0033] And / or, 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.

[0034] And / or, the counter electrode layer is a mesh-like or planar transparent conductive layer made of one or more of the following: 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.

[0035] This invention also provides a method for preparing a solvent-free acrylate electroreflective device, comprising the following steps:

[0036] S1) A metallic silver compound component, a polymerizable monomer, and an additive are mixed to obtain an electroreflective paste; the polymerizable monomer includes hydrophobic polymeric monomers of acrylates; the additive includes an ionic liquid; the molecular structure of the ionic liquid contains hydrophobic long alkyl and / or aryl functional groups.

[0037] S2A) The electroreflective paste is coated on the surface of the working electrode layer or the counter electrode layer, then combined with the counter electrode layer or the working electrode layer, and cured to obtain a solvent-free acrylate system electroreflective device.

[0038] Alternatively, S2B) provides a hollow device; 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 opposite side of the rigid first substrate and the rigid second substrate, and a counter electrode layer is provided on the opposite side of the rigid second substrate and the rigid first substrate, and a spacer is provided between the working electrode layer and the counter electrode layer to control the spacing; 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 electroreflective paste 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 electroreflective device.

[0039] This invention provides a solvent-free acrylate-based electroreflective device, comprising an electroreflective layer; the electroreflective layer is formed by curing an electroreflective paste; the electroreflective paste comprises a metallic silver compound component, polymerizable monomers, and additives; the polymerizable monomers include hydrophobic polymer monomers of acrylates. Compared with the prior art, this invention uses a solvent-free acrylate system, using acrylate molecules with hydrophobic groups as the main polymer backbone to make the integrated electroreflective layer hydrophobic, effectively improving the overall water and oxygen resistance, significantly improving the cycle stability and lifespan of the device, and simultaneously, the acrylate gel has high strength and strong adhesion, which can be used in flexible roll-to-roll processes, broadening the application fields and facilitating industrial production.

[0040] Furthermore, this invention utilizes the compatibility between ionic liquids containing long alkyl and / or aryl functional groups and acrylate monomers, providing an environment that can dissolve acrylate monomers with hydrophobic groups, while further improving the water and oxygen resistance of the electroreflective layer and the stability of the device. Attached Figure Description

[0041] Figure 1 A schematic diagram of the structure of the solvent-free acrylate electroreflective device provided by the present invention;

[0042] Figure 2 This is a schematic diagram of the transmittance testing sampling points of the electroluminescent devices obtained in Examples 1-3 and Comparative Examples 1-3 of the present invention during the cycling process. Detailed Implementation

[0043] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0044] This invention provides a solvent-free acrylate-based electroreflective device, comprising an electroreflective layer; the electroreflective layer is formed by curing an electroreflective paste; the electroreflective paste comprises a metallic silver compound component, a polymerizable monomer, and additives; the polymerizable monomer comprises a hydrophobic polymer monomer of acrylate.

[0045] In this invention, the thickness range of the electroluminescent layer is preferably 10μm to 300μm, more preferably 50μm to 200μm, even more preferably 50μm to 150μm, and most preferably 100μm.

[0046] According to the present invention, the mass of the silver compound component is preferably 1% to 30% of the mass of the electroreflective 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.

[0047] According to the present invention, the mass of the polymerizable monomer is preferably 5% to 50% of the mass of the electroreflective 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%.

[0048] 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 electroreflective 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%, 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.

[0049] 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 electroreflective 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, 2-hydroxypropyl acrylate, etc. 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.

[0050] 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, 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 electroreflective paste, 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.

[0051] According to the present invention, the mass of the additive is preferably 20% to 90% of the mass of the electroreflective 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%.

[0052] 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.

[0053] 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 electroreflective 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.

[0054] 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 electroreflective paste 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.

[0055] According to the present invention, the solvent-free acrylate electroreflective device preferably comprises a first substrate layer, a working electrode layer, an electroreflective layer, a counter electrode layer, and a second substrate layer disposed sequentially; see also Figure 1 , Figure 1This is a schematic diagram of the structure of the solvent-free acrylate electroreflective device provided by the present invention, wherein 11 is the first substrate layer, 12 is the working electrode layer, 13 is the electroreflective layer, 14 is the counter electrode layer, and 15 is the second substrate layer.

[0056] 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 may be a transparent substrate layer or a non-transparent substrate layer.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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 electroreflective 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.

[0061] This invention also provides a method for preparing the above-mentioned solvent-free acrylate electroreflective device, comprising the following steps: S1) mixing a metallic silver compound component, a polymerizable monomer, and an additive to obtain an electroreflective paste; the polymerizable monomer includes a hydrophobic polymeric monomer of acrylate; the additive includes an ionic liquid; the ionic liquid molecule contains hydrophobic long alkyl and / or aryl functional groups; S2A) coating the electroreflective paste onto the surface of a working electrode layer or a 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 electroreflective 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, and a spacer is provided between the working electrode layer and the counter electrode layer to control the spacing; 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 electroreflective paste 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 electroreflective device.

[0062] In this invention, there are no special restrictions on the source of any 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.

[0063] The electroreflective 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.

[0064] The electroluminescent paste is coated onto the surface of the working electrode layer or the counter electrode layer, and then laminated with the counter electrode layer or the working electrode layer and cured. The working electrode layer and the counter electrode layer are preferably laminated onto 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 electroluminescent device.

[0065] Alternatively, the electroreflective 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 electroreflective 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 electroreflective 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.

[0066] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a solvent-free acrylate electroreflective device and its preparation method provided by the present invention.

[0067] All reagents used in the following examples are commercially available; the molecular weight of the polyethylene glycol diacrylate used in the examples is 575.

[0068] Example 1

[0069] 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.

[0070] 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 electroreflective layer with the same thickness as the spacer particle size (i.e., 100μm).

[0071] 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.

[0072] 1.4 Roller slicing, electrode attachment, and encapsulation yield a flexible, integrated photo-solid electroluminescent device.

[0073] Example 2

[0074] A flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-dodecyl-3-methylimidazolium chloride.

[0075] Example 3

[0076] A flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-eicosyl-3-methylimidazolium chloride.

[0077] Example 4

[0078] A flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that 1-octyl-3-methylimidazolium chloride was replaced with 1-benzyl-3-methylimidazolium chloride.

[0079] Example 5

[0080] A flexible, integrated photo-solid electroreflective device was prepared according to the method of Example 1, except that butyl acrylate was replaced with lauryl acrylate.

[0081] Example 6

[0082] A flexible photo-solid integrated electroreflective device was prepared according to the method of Example 1, except that butyl acrylate was replaced with myristate acrylate.

[0083] Example 7

[0084] The flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that butyl acrylate was replaced with eicosate acrylate, and the rest was the same as in Example 1.

[0085] Comparative Example 1

[0086] A flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that butyl acrylate was replaced with acrylic acid.

[0087] Comparative Example 2

[0088] A flexible photo-solid integrated electroreflective device was prepared according to the method of Example 1, except that butyl acrylate was replaced with vinylpyrrolidone.

[0089] Comparative Example 3

[0090] A flexible photo-solid integrated electroluminescent device was prepared according to the method of Example 1, except that butyl acrylate was replaced with acrylamide.

[0091] Comparative Example 4

[0092] A flexible, photo-solid integrated electroreflective device was prepared according to the method in Example 1, 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. Because the hydrophobic acrylate monomers are not miscible with the hydrophilic ionic liquid, a transparent and homogeneous electroreflective device could not be prepared.

[0093] Comparative Example 5

[0094] A flexible, integrated photo-solid electroreflective device was prepared according to the method in Example 1, 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, homogeneous electroreflective device.

[0095] The difference in current reflectivity between the integrated electroluminescent devices obtained in Examples 1-7 and Comparative Examples 1-3 during cycling was monitored in the visible and infrared ranges (380-2500 nm). The reflectivity was measured according to the method in GB / T 33234-2016 "Test Method for Reflectivity of Photothermal Power Generation Glass Mirrors". Under the conditions of an active area of ​​100 mm × 100 mm and an electroluminescent layer thickness of 100 μm, the coloring time and fading time were determined as follows: the newly fabricated electroluminescent devices were placed in a UV-Vis spectrometer, and the average transmittance of 9 points on the device 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 electroreflective device operating at a coloring voltage (-0.6V) for time t1, followed by operation at a fading voltage (0.3V) for time t2. Transmittance tests are performed at 8 points on the edge and 1 point on the center during the cycle. Figure 2 As shown in Table 1, if the absolute value of the fading state change at any of the nine points exceeds 5%, it is considered an optical failure. The current number of cycles is recorded as the test result.

[0096] Table 1 Results of Cyclic Tests on Electroreflective Devices

[0097] Coloring time t1 (s) Fading time t2 (s) Number of cycles (times) Example 1 42 60 4800 Example 2 42 61 4800 Example 3 48 70 4900 Example 4 60 81 4850 Example 5 45 63 5200 Example 6 45 63 5250 Example 7 45 64 5260 Comparative Example 1 42 62 2000 Comparative Example 2 40 58 1800 Comparative Example 3 37 56 2300

[0098] According to the test results in Table 1, the number of cycles in Example 1 was significantly higher than that in Comparative Examples 1-3. 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 exhibits excellent water and oxygen resistance, which can effectively improve the device's cycle life.

[0099] The number of cycles in Examples 2 and 3 was the same as in Example 1, 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 4 was the same as in Example 1, 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 5-7 was higher than that in Example 1. 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 7 was the same as in Examples 5 and 6, 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 C14 and C12.

[0100] 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 2.

[0101] Table 2 Current and Current Change Rate during Electroreflective Device Cycling

[0102]

[0103] In electroluminescent 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.

[0104] According to the test results in Table 2, the current change rate of Example 1 is much smaller than that of Comparative Examples 1-3. 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 have excellent water and oxygen tolerance, effectively improving its cycle life.

[0105] The current change rate in Examples 5-7 was less than that in Examples 1, 2, 3 and 4. This result indicates that the more hydrophobic long alkyl chain acrylate monomers enhanced the device's water and oxygen tolerance and further improved its cycle stability.

[0106] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A solvent-free acrylate system electrochromic light reflecting device, characterized in that, The electroreflective layer is formed by curing an electroreflective paste; the electroreflective paste comprises a silver compound component, a polymerizable monomer, and an additive; The polymerizable monomer comprises an acrylate hydrophobic polymer monomer.

2. The solvent-free acrylate system electrochromic device according to claim 1, characterized in that, The additive comprises an ionic liquid; the molecular structure of the ionic liquid comprises a hydrophobic long alkyl and / or aryl functional group.

3. The solvent-free acrylate system electrochromic device according to claim 2, characterized in that, The mass of the ionic liquid is 5% to 50% of the mass of the electroreflective paste; The ionic liquid comprises one or more of imidazole salt ionic liquid, pyridine salt ionic liquid, pyrrole salt ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, fluorinated imidazole salt ionic liquid, fluorinated pyridine salt ionic liquid, fluorinated pyrrole salt ionic liquid, fluorinated quaternary ammonium salt ionic liquid, and fluorinated quaternary phosphonium salt ionic liquid.

4. The solvent-free acrylate system electrochromic device according to claim 2, wherein, The mass of the silver compound component is 1% to 30% of the mass of the electroreflective paste; The mass of the acrylate hydrophobic polymer monomer is 5% to 50% of the mass of the electroreflective paste; The mass of the additive is 20% to 90% of the mass of the electroreflective paste.

5. The solvent-free acrylate system electrochromic device according to claim 2, wherein, The silver compound component is 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, and silver bistrifluoromethanesulfonimide; The acrylate hydrophobic polymer monomer comprises one or more of methyl acrylate and derivatives thereof, methyl methacrylate and derivatives thereof, ethyl acrylate and derivatives thereof, ethyl methacrylate and derivatives thereof, propyl acrylate and derivatives thereof, propyl methacrylate and derivatives thereof, butyl acrylate and derivatives thereof, butyl methacrylate and derivatives thereof, n-pentyl acrylate and derivatives thereof, isopentyl acrylate and derivatives thereof, hexyl acrylate and derivatives thereof, hexyl methacrylate and derivatives thereof, n-octyl acrylate and derivatives thereof, n-octyl methacrylate and derivatives thereof, isooctyl acrylate and derivatives thereof, isooctyl methacrylate and derivatives thereof, lauryl acrylate and derivatives thereof, lauryl methacrylate and derivatives thereof, myristyl acrylate and derivatives thereof, myristyl methacrylate and derivatives thereof, cyclohexyl methacrylate and derivatives thereof, isobornyl acrylate and derivatives thereof, isobornyl methacrylate and derivatives thereof, styrene and derivatives thereof, dicyclopentenyl acrylate and derivatives thereof, benzyl acrylate and derivatives thereof, benzyl methacrylate and derivatives thereof. and / or, the ionic liquid is selected from one or more of 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-tetradecyl-3-methylimidazolium tetrafluoroborate, 1-tetradecyl-3-methylimidazolium hexafluorophosphate, 1-tetradecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexadecyl-3-methylimidazolium tetrafluoroborate, 1-hexadecyl-3-methylimidazolium hexafluorophosphate, 1-hexadecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

6. The solvent-free acrylate system electrochromic device according to claim 1, wherein, the polymerizable monomer further comprises a co-monomer; the co-monomer comprises one or more of an acrylic monomer, an acrylamide monomer, an acrylate monomer, and an olefinic derivative; and / or, the polymerizable monomer further comprises a cross-linking agent; and / or, the additive further comprises one or more of an initiator, a cross-linking agent, a coupling agent, a surfactant, a thickening agent, and a spacer.

7. The solvent-free acrylate system electrochromic device according to claim 6, characterized in that, the co-monomer comprises one or more of acrylic acid, fumaric acid, 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-imidazole and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamidododecylsulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, p-phenoxybenzyl acrylate, 2-phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, propoxylated nonylphenol acrylate, and bicyclopentanymethyl methacrylate; and / or, the cross-linking agent comprises one or more of tricyclodecane dimethanol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, tricyclodecane dimethanol dimethacrylate, 1,12-dodecanediol dimethacrylate, N,N-methylenebisacrylamide, and 2-hydroxyethyl methacrylate phosphate ester; And / or, the initiator comprises one or more of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, dibenzoyl peroxide, benzaldehyde-formaldehyde trimer, acryloyl carboxylic diester, 2,4,6(trimethylbenzoyl) diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl ethyl phosphonate, 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide, phenyl(2,4,6-trimethylbenzoyl) lithium phosphate, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 1-hydroxyphenyl cyclohexanone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone; And / or, the coupling agent comprises a silane coupling agent and / or a phthalate coupling agent; And / or, the surfactant comprises one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant; And / or, the thickening agent comprises one or more of an acrylate polyol, sodium polyacrylate, sodium poly-pentaerythritol acrylate, sodium alginate and carboxymethyl cellulose; And / or, the spacer comprises one or more of polystyrene microspheres, polyacrylate microspheres and silica microspheres.

8. The solvent-free acrylate system electrochromic device according to claim 1, wherein, It comprises a first substrate layer, a working electrode layer, an electrochromic layer, a counter electrode layer and a second substrate layer arranged in sequence.

9. The solvent-free acrylate system electrochromic device according to claim 8, characterized in that, 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; The inorganic substrate layer is selected from one or more of glass, diamond and ceramic; The organic substrate layer comprises one or more of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polyperfluoroethylene propylene, ethylene-vinyl acetate copolymer, polyimide, thermoplastic polyurethane, polysulfone and acrylonitrile-butadiene-styrene terpolymer; And / or, the working electrode layer is a grid-shaped or planar transparent conductive layer made of one or more of indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, metal copper, metal silver, metal aluminum, metal gold, indium tin oxide-copper multilayer composite, indium tin oxide-silver multilayer composite, indium tin oxide-aluminum multilayer composite, indium tin oxide-gold multilayer composite, graphene and carbon nanotube; And / or, the counter electrode layer is a grid-shaped or planar transparent conductive layer made of one or more of nano-copper wire, nano-silver wire, nano-aluminum wire, metal copper, metal silver, metal aluminum, indium tin oxide-copper multilayer composite, indium tin oxide-silver multilayer composite, indium tin oxide-aluminum multilayer composite and nano-silver paste material.

10. A process for the preparation of a solvent-free acrylate system electrochromic device, characterized in that, It comprises the following steps: S1) mixing a silver compound component, polymerizable monomers and additives to obtain an electrochromic paste; the polymerizable monomers comprise acrylate hydrophobic polymer monomers; the additives comprise ionic liquids; the molecular structure of the ionic liquids comprises hydrophobic long alkyl and / or aryl functional groups; S2A) coating the electrochromic paste on the surface of the working electrode layer or the counter electrode layer, and then compounding with the counter electrode layer or the working electrode layer, and curing to obtain a solvent-free acrylate system electrochromic device; Alternatively, S2B) providing a hollow device; the hollow device comprises a rigid first substrate and a rigid second substrate arranged face to face, the rigid first substrate and the rigid second substrate are provided with a working electrode layer on the opposite side, the rigid second substrate and the rigid first substrate are provided with a counter electrode layer on the opposite side, and a spacer is arranged between the working electrode layer and the counter electrode layer to control the distance; the rigid first substrate or the rigid second substrate is provided with a preformed hole, and the hollow device is a closed device except for the preformed hole; the electrochromic paste is injected into the hollow device between the working electrode and the counter electrode through the preformed hole, and is cured to obtain a solvent-free acrylate system electrochromic device.

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