Copper-element-containing in-situ photocurable electro-reflective slurry and preparation method and application thereof

Abstract

The invention provides an in-situ photocurable electro-reflective slurry containing a copper element. The in-situ photocurable electro-reflective slurry comprises a metal source, a polymerizable monomer, a photoinitiator and an additive, the metal source comprises copper in the form of ions; the polymerizable monomer contains a group capable of being coordinated with copper existing in an ionic form. The polymerizable monomer is matched with copper existing in an ion form in molar weight, contains a functional group which can be rapidly complexed and coordinated with the copper existing in the ion form, and can form a relatively stable chelate in a polymerization process, so that the copper does not play a role of a free radical inhibitor in a photo-initiated polymerization process any more; therefore, the polymerization reaction is smoothly carried out and tends to be complete. The electro-reflective device manufactured by using the slurry has the characteristics of simple manufacturing process, good process stability reproducibility, rapid in-situ photopolymerization, low cost, good mechanical strength, high transmittance in a fading state, high reflectivity in a coloring state, good cycling stability of a copper-mediated device existing in an ion form, and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electrochromic devices, and particularly relates to an in-situ photocurable electrochromic paste containing copper element and a preparation method and application thereof. BACKGROUND

[0002] Electrochromic devices generally refer to the stable and reversible color change of the optical properties such as reflectivity, transmittance and absorptivity of a material by applying an external electric field, so as to actively and dynamically control the light and solar radiation heat.

[0003] Although the traditional absorption type electrochromic device can realize the change of transmittance by applying an external electric field, the change of reflectivity is small. The new generation of electrochromic technology is that under the action of an external electric field, the metal cations in the active layer are reduced on the electrode plate to form a dense and uniform metal film. Based on the characteristics of the metal itself, the metal film can reflect all or part of the visible light, infrared and near-infrared, ultraviolet and other wave bands back, has a large transmittance and reflectivity control window, and is an active light and heat management control technology.

[0004] To achieve electroluminescent devices with high visible light transmittance, good mechanical properties, and high safety in the faded state, a high-transmittance transparent electrode ITO is used as the working electrode, and a high-transmittance metal mesh is used as the counter electrode, with a gel-state or solid electrolyte filled in between. When using an electrolyte made with a paste containing copper ions in the middle, the device exhibits good cycle stability and can return to its initial state after multiple fades. For example, if only bismuth ions are used in the device, when bismuth is deposited on the working electrode ITO, during dedeposition, the deposited bismuth cannot be completely dissolved back into the electrolyte layer through a single electrochemical process. After each cycle, a trace amount of bismuth always remains on the working electrode ITO and cannot be removed. This cycle repeats, causing unremoved bismuth to accumulate on the ITO, gradually reducing the device's transmittance in the faded state. Furthermore, following the law of charge conservation, the metal content on the metal mesh serving as the counter electrode gradually decreases and thins, even leading to localized open circuits in some areas. This rapidly accelerates the degradation of the device's optical and electrical performance, ultimately resulting in reduced cycle stability and a significant decrease in the number of cycles. In contrast, if both bismuth and copper ions are used in the device, the copper ions mediate the reaction of bismuth ions during both deposition and removal. This allows the copper-bismuth alloy to completely transform into its ionic form during the removal and dissolution process after deposition on the working electrode, dissolving back into the electrolyte layer. Ultimately, the device's optical performance shows almost no degradation after multiple cycles. However, due to the quenching effect of copper ions on polymer radicals, slurries containing copper ions cannot be photocured (existing reported electroreflective devices containing copper ions are all in liquid or semi-gel state, and most are formed by solution immersion, solvent evaporation, or high-temperature thermosetting). This results in complex and cumbersome fabrication of devices using slurries containing copper ions, poor mechanical properties, low safety performance, and high manufacturing costs. This technical field has lacked in-situ photocurable electroreflective slurries containing copper in ionic form. This paper aims to provide an in-situ photocurable electroreflective slurry containing copper in ionic form to solve the technical bottleneck problem of the inability to photocur slurries containing copper in ionic form in the industry. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide an electroreflective paste containing copper that can be cured in situ, its preparation method and application. The electroreflective paste can be cured by light, and the devices made using it have the characteristics of simple manufacturing process, good process stability, low cost, good mechanical strength, high safety, high transmittance in the faded state, high reflectivity in the colored state, and good cycle stability.

[0006] This invention provides an in-situ photocurable electroreflective paste containing copper, comprising a metal source, a polymerizable monomer, a photoinitiator, and additives;

[0007] The metal source contains copper in ionic form;

[0008] The polymerizable monomer contains groups that coordinate with copper in ionic form and form stable chelates with copper in ionic form during polymerization.

[0009] Preferably, the group is selected from one or more of amide, amino, imino, hydroxy, carboxyl, phosphate, phosphite and mercapto.

[0010] Preferably, the copper existing in ionic form is one or more of the following: copper ion, cuprous ion, tetrachlorocuprate ion, tetrahydrated copper ion, tetraamminecuprate ion, tetraethyl cyanidecuprous ion, and any copper complex ion formed by reacting the above ions.

[0011] Preferably, the molar ratio of copper in ionic form to polymerizable monomers is 1:0.5 to 1:10000.

[0012] Preferably, the polymerizable monomer is selected from compounds shown in Formula 101 and / or Formula 102.

[0013]

[0014]

[0015] Wherein, R1 and R4 are independently selected from hydrogen atoms or methyl groups; R2, R3 and R5 are independently selected from hydrogen atoms, C1-C10 aliphatic alkane chains or substituted alkyl groups, wherein the substituted group in the substituted alkyl group is selected from one or more of amino, imino, hydroxy, carboxyl, phosphate, phosphite, mercaptocarboxyl, ether, aldehyde, carbonyl, halogen and aryl; R6 is a C1-C10 aliphatic alkane chain or substituted alkyl group, wherein the substituted group in the substituted alkyl group is selected from one or more of amino, imino, hydroxy, carboxyl, phosphate, phosphite, mercaptocarboxyl, ether, aldehyde, carbonyl, halogen and aryl.

[0016] Preferably, the compound represented by Formula 101 is selected from one or more of acrylamide, N-methylmethacrylamide, N,N-bis(2-hydroxyethyl)methacrylamide, 3-methacrylamide propionic acid, phosphorous acrylate monomer, and acrylamide-polyethylene glycol-mercapto, and the compound represented by Formula 102 is selected from one or more of N,N'-methylenebisacrylamide, N,N'-1,4-succinodimethicone[N-[3-(phosphooxy)propyl]-2-acrylamide], N,N'-1,4-succinodimethicone[N-(2-hydroxyethyl)-2-acrylamide], and N,N'-methylenebismethylacrylamide.

[0017] Preferably, the polymerizable monomer further includes a non-coordinated chelating monomer; the non-coordinated chelating monomer is selected from monomers containing one or more groups of olefinic, alkyneic and epoxy groups, which cannot form a stable chelate with copper in ionic form during polymerization.

[0018] Preferably, the olefin-containing monomer is selected from one or more of acrylates, acrylics, acryloyls, olefin-based pyrrolidones, olefin-based silanes, and vinyl-containing ionic liquids.

[0019] Preferably, the metal source further includes a second metal source in addition to a copper metal source existing in ionic form;

[0020] The second metal source includes one or more of the following: silver in ionic form, bismuth in ionic form, zinc in ionic form, gold in ionic form, aluminum in ionic form, iron in ionic form, and titanium in ionic form.

[0021] The molar ratio of the metal source in ionic form to the copper in ionic form in the second metal source is 100:1 to 1:1000.

[0022] Preferably, the photoinitiator is selected from photoinitiator 2959, photoinitiator TPO, photoinitiator 184, photoinitiator 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, and benzoin... One or more of the following: isopropyl ether, benzoyl butyl 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, thiopropoxythioxanthone, isopropylthioxanthone, fluorinated diphenyltitanium, bis(pentafluorophenyl)titanium, and photoinitiator LAP.

[0023] Preferably, the additive contains a diluent and / or a leveling agent;

[0024] 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-ethyl-3-methylimidazolium chloride), (1-butyl-3-methylimidazolium bromide), (1-ethyl-3-methylimidazolium bromide), (1-butyl-2,3-dimethylimidazolium chloride), and 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, N-methylethylpiperidine bromide, N-methyl 1-Butylpiperidine 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, 1-epoxy One or more of the following: propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, (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.

[0025] The leveling agent includes one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, N,N-diethylpropyne 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.

[0026] This invention provides a method for preparing an in-situ photocurable electroreflective paste containing copper in ionic form, as described in the above-mentioned technical solution, comprising the following steps:

[0027] The metal source, polymerizable monomer, photoinitiator and additives are mixed evenly to obtain an electroreflective paste that can be cured in situ by photopolymerization.

[0028] Specifically, the metal source, polymerizable monomer, and additives are mixed at 95–105°C to form a homogeneous solution, and then cooled to room temperature for storage. Before use, the slurry is heated to 55–65°C, a photoinitiator is added, and the solution is completely and uniformly dissolved to obtain an electroreflective slurry that can be cured in situ.

[0029] This invention provides an electroluminescent device, comprising a first substrate layer, a working electrode layer, an integrated electroluminescent layer, a counter electrode layer, and a second substrate layer arranged sequentially.

[0030] The integrated electroreflective layer is formed by photocuring the electroreflective paste described in the above technical solution.

[0031] This invention provides an in-situ photocurable electroreflective paste containing copper, characterized by comprising a metal source, a polymerizable monomer, a photoinitiator, and additives; the metal source contains copper in ionic form; the polymerizable monomer contains groups capable of coordinating with the ionic copper and forming stable chelates with it during polymerization. The electroreflective paste provided by this invention includes polymerizable monomers that match the molar amount of ionic copper, rapidly complexing with it and forming stable chelate systems during polymerization. This prevents the ionic copper from acting as a free radical inhibitor during photo-initiated polymerization, allowing the polymerization reaction to proceed smoothly and reach near-complete completion. When the aforementioned polymerizable monomer, capable of performing a specific function, is added to an electroreflective device system, the paste can be rapidly and conveniently photocured in situ. Devices made using this paste feature simple fabrication, good process stability, low cost, high mechanical strength, high safety performance, high transmittance in the faded state, high reflectivity in the colored state, and good cycle stability. By realizing a photocurable electroluminescent device containing copper, it is possible to achieve excellent performance in the faded state with visible light transmittance of over 80% and reflectivity of less than 15%; in the colored state, visible light transmittance is reduced to less than 5% and reflectivity can reach over 90%, with a cycle life of over 5000 times. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the structure of an electroluminescent device; wherein, 11 is the first substrate layer, 12 is the working electrode layer, 13 is the integrated electroluminescent layer, 14 is the counter electrode layer, and 15 is the second substrate layer.

[0033] Figure 2 An electrochemical cycle test diagram of the electroreflective device prepared in Example 10;

[0034] Figure 3 This is a real-life photograph demonstrating the performance of the device prepared in Example 10 of the present invention. The left side shows the colored state of device A, and the right side shows the faded state of device B. Detailed Implementation

[0035] This invention provides an in-situ photocurable electroreflective paste containing copper, comprising a metal source, a polymerizable monomer, a photoinitiator, and additives;

[0036] The metal source contains copper in ionic form;

[0037] The polymerizable monomer contains groups that coordinate with copper in ionic form and can form stable chelates with copper in ionic form during polymerization.

[0038] The electroreflective paste provided by this invention includes polymerizable monomers that match the amount of copper present in ionic form, containing functional groups capable of rapidly complexing and coordinating with the ionic copper and forming a stable chelate system during polymerization. This prevents the ionic copper from acting as a free radical inhibitor during photo-initiated polymerization, allowing the polymerization reaction to occur smoothly and tend towards complete completion. After the ionic copper and polymerizable monomers are added to the electroreflective device system, the paste can be rapidly and conveniently photocured. Furthermore, the metal deposited on the transparent working electrode ITO can be smoothly and completely de-deposited and redissolved back into the electrolyte layer under the mediation of the ionic copper during multiple cycles, ultimately greatly slowing down the degradation of the device's optical performance. This results in a significant increase in the device's cycle life and cycling stability. Simultaneously, the convenience of in-situ photocuring makes device fabrication more convenient and controllable. The fully cured device does not leak electrolyte, enhancing its safety performance.

[0039] The electroreflective paste provided by this invention includes a metal source; the metal source comprises copper in ionic form. During polymerization, the copper in ionic form coordinates with groups in polymerizable monomers to form relatively stable chelates, so that the copper in ionic form no longer acts as a free radical inhibitor during UV light-induced polymerization, thereby allowing the polymerization reaction to occur smoothly and tend to be complete.

[0040] In this invention, the copper present in ionic form is preferably one or more of copper ions, cuprous ions, cupric tetrachloroacetate ions, cupric tetrahydrate ions, cupric tetraamminecopper ions, and cupric tetraethyl cyanide ions. The sources of the copper in the above-mentioned ionic forms can be copper chloride, cuprous chloride, copper sulfate, cuprous sulfate, tetramethylamine tetrachlorocuprate, potassium tetrachlorocuprate, etc.

[0041] The metal source described in this invention further includes a second metal source; the second metal source includes one or more of silver, bismuth, zinc, gold, aluminum, iron, and titanium in ionic form.

[0042] The silver in ionic form is selected from one or more of silver chloride, silver bis(trifluoromethanesulfonyl)imide, silver oxide, and silver sulfate.

[0043] The bismuth present in ionic form is selected from one or more of bismuth chloride, bismuth sulfate, bismuth nitrate, bismuth oxide, and bismuth sulfide.

[0044] The zinc present in ionic form is selected from one or more of zinc chloride, zinc sulfate, zinc sulfide, zinc hydroxide, zinc oxide, and zinc nitrate.

[0045] The gold present in ionic form is selected from one or more of gold chloride, gold oxide, gold hydroxide, gold oxide, gold sulfide, gold cyanide, and gold iodide.

[0046] The aluminum present in ionic form is selected from one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, and aluminum chloride.

[0047] Iron in ionic form is selected from one or more of the following: ferrous oxide, ferrous oxide, iron(II,III) oxide, ferrous hydroxide, ferrous hydroxide, ferrous sulfide, ferric chloride, ferrous chloride, ferrous sulfate, ferrous nitrate, and ferrous lactate.

[0048] Titanium in ionic form is selected from one or more of titanium dioxide, titanium tetrachloride, barium metatitanate, titanium nitrate, and organotitanium compounds.

[0049] In a specific embodiment of the present invention, the second metal source is selected from silver chloride or silver bis(trifluoromethanesulfonyl)imide.

[0050] In this invention, the molar ratio of the metal source existing in ionic form to the copper existing in ionic form in the second metal source is 100:1 to 1:1000; preferably 50:1 to 1:100, and more preferably 10:1 to 1:100.

[0051] The electroreflective paste provided by this invention comprises a polymerizable monomer; the polymerizable monomer contains a group that can coordinate with copper in ionic form. The polymerizable monomer is a monomer capable of forming a stable chelate system with copper in ionic form during polymerization. The group in the polymerizable monomer of this invention that coordinates with copper in ionic form is selected from one or more of amide, amino, imine, hydroxyl, carboxyl, phosphate, phosphite, and mercapto groups.

[0052] The polymerizable monomers described in this invention are selected from compounds represented by Formula 101 and / or Formula 102.

[0053]

[0054]

[0055] Wherein, R1 and R4 are independently selected from hydrogen atoms or methyl groups; R2, R3 and R5 are independently selected from hydrogen atoms, C1-C10 aliphatic alkane chains or substituted alkyl groups, wherein the substituted group in the substituted alkyl group is selected from one or more of amino, imino, hydroxy, carboxyl, phosphate, phosphite, mercaptocarboxyl, ether, aldehyde, carbonyl, halogen and aryl; R6 is a C1-C10 aliphatic alkane chain or substituted alkyl group, wherein the substituted group in the substituted alkyl group is selected from one or more of amino, imino, hydroxy, carboxyl, phosphate, phosphite, mercaptocarboxyl, ether, aldehyde, carbonyl, halogen and aryl.

[0056] In specific embodiments of the present invention, the polymerizable monomer of formula 101 is selected from one or more of acrylamide, N-methylmethacrylamide, N,N-bis(2-hydroxyethyl)methacrylamide, 3-methacrylamide propionic acid, phosphorous acrylate monomer, and acrylamide-polyethylene glycol-mercapto. The compound of formula 102 is selected from one or more of N,N'-methylenebisacrylamide, N,N'-1,4-succinodimethicone[N-[3-(phosphooxy)propyl]-2-acrylamide], N,N'-1,4-succinodimethicone[N-(2-hydroxyethyl)-2-acrylamide], and N,N'-methylenebismethylacrylamide.

[0057] The electroreflective paste provided by this invention further includes non-coordinating chelating monomers in its polymerizable monomers. These non-coordinating chelating monomers are selected from monomers containing one or more groups of olefin, alkyne, and epoxy groups, and cannot form stable chelates with copper in ionic form during polymerization. The olefin-containing monomers are selected from one or more of acrylates, acrylics, acryloyl groups, olefin-based pyrrolidones, olefin-based silanes, and vinyl-containing ionic liquids. The function of these non-coordinating chelating monomers is to copolymerize with the aforementioned monomers that can coordinate with copper in ionic form to form a stable, integrated electroreflective layer. After adding these non-coordinating chelating monomers, the functional layer formed after the paste cures exhibits good film-forming properties and excellent mechanical properties, with superior ion transport efficiency, resulting in better stress properties of the device and faster, more stable color change.

[0058] In specific embodiments of the present invention, the non-coordinating chelating monomer is selected from one or more of ethyl acrylate, ethylene glycol dimethacrylate, isobornyl acrylate, 2-methoxyethyl acrylate, polyethylene glycol diacrylate, trifluoroethyl acrylate, and 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt.

[0059] The electroreflective paste provided by this invention includes a photoinitiator, which comprises an ultraviolet photoinitiator and / or a visible light photoinitiator. The photoinitiator in this invention is capable of initiating the polymerization reaction of polymerizable monomers. The photoinitiator is selected from 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... The product comprises 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.

[0060] The electroreflective paste provided by this invention includes additives; the additives are selected from diluents and / or leveling agents. The diluent's function is to dissolve the metal source and increase the ionic conductivity of the electrolyte in the paste and inhibit the precipitation reaction on the electrode surface, thereby improving the electrodeposition quality of the electroreflective paste; the diluent is preferably selected from 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide salt, chlorinated (1-butyl-3-methylimidazolium), 1-n-butyl-1-methylpyrrolidine di(trifluoromethanesulfonyl)imide, chlorinated (1-ethyl-3-methylimidazolium), brominated (1-butyl-3-methylimidazolium), brominated (1-ethyl-3-methylimidazolium), chlorinated (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, Trimethylhydroxyethylamine chloride, N-Methylethylpiperidine bromide, N-Methylbutylpiperidine bis(trifluoromethanesulfonylimide), Chloride (N-methylbutylpyrrolidine), Bromide (N-methylbutylpyrrolidine), N-Methylethylmethanesulfonate, Bromide Methyl ethyl morpholine, N-methylpropyl morpholine bis(trifluoromethanesulfonyl)imide salt, methyl tributylphosphine tetrafluoroborate, methyl tributylphosphine hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, (1-epoxypropyl-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 are selected from one or more of these. The leveling agent, during electrodeposition, adsorbs onto the substrate surface, inhibiting the electrodeposition process and thus promoting surface smoothing. The leveling agent used in this invention is selected from 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.

[0061] The present invention requires controlling the content of copper in ionic form so that it can achieve better technical effects within the following dosage range; the molar ratio of copper in ionic form to polymerizable monomer is 1:2 to 1:10, preferably 1:2 to 1:8, and more preferably 1:4 to 1:8.

[0062] This invention provides a method for preparing the copper-containing, in-situ photocurable electroreflective paste described in the above-mentioned technical solution, comprising the following steps:

[0063] The metal source, polymerizable monomer, photoinitiator and additives are mixed evenly to obtain an electroreflective paste that can be cured in situ by photopolymerization.

[0064] The present invention preferably involves uniformly mixing the metal source, polymerizable monomer, and additives under heating and stirring conditions.

[0065] Specifically, the metal source, polymerizable monomer, and additives are mixed at 95–105°C to form a homogeneous solution, and then cooled to room temperature for storage. Before use, the slurry is heated to 55–65°C, a photoinitiator is added, and the solution is completely and uniformly dissolved to obtain an electroreflective slurry that can be cured in situ.

[0066] The method for preparing electroreflective paste provided by the present invention is simple and easy to industrialize.

[0067] This invention provides an electroluminescent device, comprising a first substrate layer, a working electrode layer, an integrated electroluminescent layer, a counter electrode layer, and a second substrate layer arranged sequentially.

[0068] The integrated electroreflective layer is formed by photocuring the electroreflective paste described in the above technical solution.

[0069] See the schematic diagram of the electroluminescent device. Figure 1 Among them, 11 is the first substrate layer, 12 is the working electrode layer, 13 is the integrated electroluminescent layer, 14 is the counter electrode layer, and 15 is the second substrate layer.

[0070] The electroreflective device provided by the present invention uses the above-mentioned electroreflective paste to form an integrated electroreflective layer. The copper ions in the integrated electroreflective layer can greatly slow down the optical performance degradation of the device and improve the cycle stability of the device when metal electrodeposition is performed on a transparent working electrode such as ITO.

[0071] In this invention, the thickness of both the first substrate layer and the second substrate layer is in the range of 50–300 μm, preferably 100–200 μm; more preferably, the thickness of both the first substrate layer and the second substrate layer is 125 μm.

[0072] The thickness of the working electrode layer ranges from 5 to 500 nm, preferably from 50 to 200 nm; more preferably, the thickness of the working electrode layer is 100 nm.

[0073] The thickness of the counter electrode layer ranges from 1 to 30 μm, preferably from 5 to 10 μm; more preferably, the thickness of the counter electrode layer is 7 μm.

[0074] The thickness of the integrated electroluminescent layer ranges from 10 μm to 500 μm, preferably from 50 to 200 μm; more preferably, the thickness of the integrated electroluminescent layer is 100 μm.

[0075] The working electrode of the electroluminescent device provided by the present invention is a transparent working electrode ITO-PET film, and the counter electrode is a grooved PET film with organic silver paste.

[0076] The preparation process of the electroreflective paste in this invention is as follows: a metal source, polymerizable monomer, and additives are mixed at 100°C to form a homogeneous solution, and then cooled to room temperature for storage. Before use, the paste is heated to 60°C, a photoinitiator is added, and the solution is completely and uniformly dissolved to obtain an electroreflective paste that can be cured in situ.

[0077] The electroluminescent device structure and fabrication method of this invention: The working electrode is a transparent ITO-PET film, and the counter electrode is a grooved PET film with organic silver paste. A flexible device is fabricated using a coating and lamination method. The thickness of the active layer is controlled by pre-adding spacer particles to the pre-curing reflective paste; the spacer particle sphere diameter is 100 micrometers. Immediately after roll-to-roll coating and lamination, the device is exposed to a UV lamp (18mW / cm²). 2 The curing process was carried out, with the curing time varying depending on the slurry formulation. After production, the films were cut into 20*30cm thin-film devices and then encapsulated using UV-curing adhesive. Finally, the ITO electrode side was placed on the glass, and the experimental observation surface was the ITO side. All preparation and processing were conducted at room temperature. For all examples and comparative examples, two 20cm*30cm devices were fabricated and experimental records were kept (labeled A and B respectively).

[0078] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, provides a copper-containing in-situ photocurable electroreflective paste, its preparation method, and its application. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0079] For all embodiments and comparative examples, two 20cm*30cm devices were fabricated and experimental records were made (referred to as A and B respectively).

[0080] In all embodiments, the polymerizable monomeric compound of formula 101 of the present invention is preferably selected from one or more of acrylamide, N-methylmethacrylamide, N,N-bis(2-hydroxyethyl)methacrylamide, 3-methacrylamide propionic acid, phosphorous acrylate monomer, and acrylamide-polyethylene glycol-mercapto. The polymerizable monomeric compound of formula 102 of the present invention is preferably selected from one or more of N,N'-methylenebisacrylamide, N,N'-1,4-succinodimethicone[N-[3-(phosphooxy)propyl]-2-acrylamide], N,N'-1,4-succinodimethicone[N-(2-hydroxyethyl)-2-acrylamide], and N,N'-methylenebismethylacrylamide.

[0081] Example 1

[0082] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0083] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g acrylamide;

[0084] Photoinitiator: Photoinitiator 2959 0.4g;

[0085] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium) and 0.1g of polyvinylpyrrolidone;

[0086] Comparative Example 1

[0087] The difference from Example 1 is that the polymerizable monomer does not include acrylamide and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0088] Example 2

[0089] Metal source: 1.3 g of silver bis(trifluoromethanesulfonyl)imide and 0.1 g of cuprous chloride;

[0090] Polymerizable monomers: isoborneol acrylate 1.5g, 2-methoxyethyl 2-acrylate 4.5g, polyethylene glycol diacrylate 0.5g, N-methylmethacrylamide 1g;

[0091] Photoinitiators: Photoinitiator 184 0.1g, Photoinitiator TPO 0.3g;

[0092] Additives: 12.6g of 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide salt and 0.1g of polyvinyl alcohol.

[0093] Comparative Example 2

[0094] Compared to Example 2, the difference is that N-methylmethacrylamide is not included in the polymerizable monomers, and it is replaced with 0.25g of isobornyl acrylate and 0.75g of 2-methoxyethyl acrylate by equal mass to ensure that the solid content is the same between the slurries.

[0095] Example 3

[0096] Metal source: 1.3g silver chloride, 0.1g cuprous chloride;

[0097] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g N,N-bis(2-hydroxyethyl)methacrylamide;

[0098] Photoinitiator: Photoinitiator 2959 0.4g;

[0099] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium) and 0.1g of hydroxyethyl cellulose;

[0100] Comparative Example 3

[0101] Compared with Example 3, the difference is that the polymerizable monomer does not include N,N-bis(2-hydroxyethyl)methacrylamide, and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0102] Example 4

[0103] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0104] Polymerizable monomers: isoborneol acrylate 1.5g, 2-methoxyethyl 2-acrylate 4.5g, polyethylene glycol diacrylate 0.5g, 3-methacrylamide propionic acid 1g;

[0105] Photoinitiator: 0.1g photoinitiator 184, 0.3g photoinitiator TPO;

[0106] Additives: 12.6g of 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide salt and 0.1g of N,N'-diethylpropynylamine sulfate.

[0107] Comparative Example 4

[0108] Compared with Example 4, the difference is that the polymerizable monomer does not include 3-methacrylamide propionic acid, and is replaced by an equal mass of 0.25 g of isobornyl acrylate and 0.75 g of 2-methoxyethyl acrylate to ensure that the solid content is the same between the slurries.

[0109] Example 5

[0110] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0111] Polymerizable monomers: 6g trifluoroethyl acrylate, 1g N,N'-1,4-succinobis[N-[3-(phosphooxy)propyl]-2-acrylamide];

[0112] Photoinitiators: 0.2g photoinitiator 2959, 0.2g photoinitiator TPO;

[0113] Additives: 12.6g of 1-n-butyl-1-methylpyrrolidine di(trifluoromethylsulfonyl)imide and 0.1g of poly(sodium 4-styrenesulfonate and maleic acid) copolymer.

[0114] Comparative Example 5

[0115] Compared with Example 5, the difference is that the polymerizable monomer does not include N,N'-1,4-succinylbis[N-[3-(phosphooxy)propyl]-2-acrylamide], and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0116] Example 6

[0117] Metal source: 1.3g silver chloride, 0.1g tetramethylamine tetrachlorocuprate;

[0118] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g phosphorus amide monomer;

[0119] Photoinitiator: Photoinitiator 2959 0.4g;

[0120] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium), 0.1g of a copolymer of 1-vinylimidazolium and 1,4-butanediol glycidyl ether;

[0121] Comparative Example 6

[0122] Compared to Example 6, the difference is that the polymerizable monomer does not include phosphorus acrylate monomer, and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0123] Example 7

[0124] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0125] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g N,N'-1,4-succinodi[N-(2-hydroxyethyl)-2-acrylamide];

[0126] Photoinitiator: Photoinitiator 2959 0.4g;

[0127] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium) and 0.1g of polyvinylpyrrolidone;

[0128] Comparative Example 7

[0129] The difference from Example 7 is that the polymerizable monomer does not include N,N'-1,4-succinyl di[N-(2-hydroxyethyl)-2-acrylamide], and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0130] Example 8

[0131] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0132] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g acrylamide-polyethylene glycol-mercapto-acrylamide;

[0133] Photoinitiator: Photoinitiator 2959 0.4g;

[0134] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium) and 0.1g of polyvinylpyrrolidone;

[0135] Comparative Example 8

[0136] Compared to Example 8, the difference is that the polymerizable monomer does not include acrylamide-polyethylene glycol-mercapto, and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0137] Example 9

[0138] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0139] Polymerizable monomers: 6g ethyl acrylate, 0.5g ethylene glycol dimethacrylate, 1g N,N'-methylenebismethylpropenylamine;

[0140] Photoinitiator: Photoinitiator 2959 0.4g;

[0141] Additives: 12.6g of chlorinated (1-butyl-3-methylimidazolium) and 0.1g of polyvinylpyrrolidone;

[0142] Comparative Example 9

[0143] The difference from Example 9 is that the polymerizable monomer does not include N,N'-methylenebismethylpropyleneamine, and is replaced with an equal mass of 1g of ethyl acrylate to ensure that the solid content is the same between the slurries.

[0144] After the electroreflective pastes prepared in Examples 1-9 and Comparative Examples 1-9 were fabricated into devices using the above-described device fabrication method, they were subjected to sufficient and appropriate UV irradiation, the time was recorded, and the curing was observed. The results are shown in Table 1. In the devices, the thicknesses of the first substrate layer, the working electrode layer, the integrated electroreflective layer, the counter electrode layer, and the second substrate layer are 125 μm, 100 nm, 100 μm, 7 μm, and 125 μm, respectively.

[0145] Table 1 UV Irradiation Time and Curing Status of Electroreflective Paste

[0146]

[0147]

[0148]

[0149] Note: In the curing status, Y represents cured, exhibiting a tough gel state; N represents uncured, exhibiting a low-viscosity, fluid liquid; UV post-lighting time refers to the time during which the uncured slurry is exposed to light again; in the post-curing status, N represents uncured, exhibiting a low-viscosity, fluid liquid; -- represents no record for this item.

[0150] Example 10

[0151] Metal source: 1.3g silver chloride, 0.1g copper chloride;

[0152] Polymerizable monomers: 6g of 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, 1g of N,N'-methylenebisacrylamide;

[0153] Photoinitiators: Photoinitiator 2959 0.1g, Photoinitiator TPO 0.3g;

[0154] Additives: 4.2g of (1-ethyl-3-methylimidazolium chloride), 8.4g of 1-n-butyl-1-methylpyrrolidine di(trifluoromethylsulfonyl)imide, and 0.1g of polyethylene glycol.

[0155] The present invention uses the slurry obtained in Example 10 to fabricate two parallel devices, denoted as Device A and Device B, according to the above-described device structure and fabrication method. In these devices, the thicknesses of the first substrate layer, working electrode layer, integrated electroreflective layer, counter electrode layer, and second substrate layer are 125 μm, 100 nm, 100 μm, 7 μm, and 125 μm, respectively. The present invention performs fading optical tests on Device A and Device B, and the results are shown in Table 2.

[0156] Table 2. Optical results of device fading in Example 10

[0157]

[0158] Comparative Example 10

[0159] Compared with Example 10, the difference is that the metal source does not contain copper chloride, and is replaced with an equal mass of 0.1g of silver chloride to ensure that the metal source ion concentration is the same between the slurries.

[0160] The present invention uses the slurries prepared in Example 10 and Comparative Example 10 to fabricate devices using the electroluminescent device structure and fabrication method described above. The present invention uses the following testing method to test the number of cycles of the devices:

[0161] In room temperature air, a simple voltage-driven cycling method is used: voltage A for coloring for t1 seconds, and voltage B for decolorizing for t2 seconds. Voltage A is determined by the peak value of the reduction peak in the cyclic voltammetry curve of the ITO working electrode corresponding to the device, measured by an electrochemical workstation (scan rate 10 mV / s), and voltage B is 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 is 60%. Figure 2 Then by Figure 2 The peak values ​​revealed that the coloring voltage A of the device made from the slurry prepared in Example 10 was -1.4V, and the fading voltage B was 1.3V. One cycle of coloring and fading was defined as 60% of the change in transmittance at 550nm. 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 electrochemical failure occurred (i.e., the device current remained below 3*10⁻⁶ during the coloring and fading process), the coloring voltage was determined. -4 If A is reached, the cycle test is considered complete, and the number of cycles at this point represents the device's lifespan.

[0162] The present invention uses the above test cycle number method to test the device lifetime, and the results are shown in Table 3.

[0163] The devices prepared from the electroreflective pastes in Example 10 and Comparative Example 10 were both exposed to UV light for 180 s, and both reached a cured, resilient gel state. A photograph demonstrating the colorfastness of the device from Example 10 is shown below. Figure 3 .

[0164] Table 3 shows the fading condition and cycle test results of the devices in Example 10 and Comparative Example 10.

[0165] Example Coloring voltage Fading voltage Fading condition Cycle number Example 10-A -1.4V 1.3V Y 5103 times Example 10-B -1.4V 1.3V Y 5021 times Comparative Example 10-A -1.4V 1.3V N 521 times Comparative Example 10-B -1.4V 1.3V N 476 times

[0166] Note: In the fading situation, Y represents complete fading each time; N represents incomplete fading each time, with a light gray substance remaining after the fading process is completed. Sufficient fading time is given in each fading process until the transmittance no longer changes.

[0167] As can be seen from all the above embodiments, the present invention provides an in-situ photocurable electroreflective paste containing copper, comprising a metal source, a polymerizable monomer, a photoinitiator, and additives; the metal source contains copper in ionic form; the polymerizable monomer contains groups that can coordinate with copper in ionic form. The reflective paste provided by the present invention includes polymerizable monomers that are matched in amount to copper in ionic form, contain functional groups that can rapidly complex and coordinate with copper in ionic form, and can form a stable chelate system during polymerization. This prevents copper in ionic form from acting as a free radical inhibitor during photo-initiated polymerization, allowing the polymerization reaction to occur smoothly and tend towards complete reaction. After copper in ionic form is added to the electroreflective device system, the metal deposited on the transparent working electrode ITO can be smoothly and completely de-deposited and redissolved back into the electrolyte layer during multiple cycles, ultimately greatly slowing down the degradation of the device's optical performance, thereby significantly increasing the device's cycle life, i.e., significantly improving the device's cycle stability. The device can also achieve high transmittance in the faded state and high reflectivity in the colored state. By realizing photocuring of copper ions, an electrochromic device can achieve excellent performance with visible light transmittance of over 80% and reflectance of less than 15% in the faded state, and visible light transmittance of less than 5% and reflectance of over 90% in the colored state, with a cycle life of over 5000 times.

[0168] 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. An in-situ photocurable electrochromic paste containing copper elements, characterized in that, The metal source, polymerizable monomer, photoinitiator and additive; The metal source comprises copper in ionic form; The polymerizable monomer contains a group capable of coordinating with the copper in ionic form and capable of forming a stable chelate with the copper in ionic form during polymerization.

2. The electrochromic paste of claim 1, wherein, The group is selected from one or more of amido, aminyl, imido, hydroxyl, carboxyl, phosphato, phosphito and mercapto.

3. The electrochromic paste of claim 1, wherein, The copper in ionic form is in one or more of the forms of copper ion, cuprous ion, tetrachlorocuprate ion, tetrachlorohydrate ion, tetraamminecuprate ion, tetraethylnitrile cuprous ion and any copper complex ion formed by using the above ions as reactants.

4. The electrochromic paste of claim 1, wherein, The molar ratio of the copper in ionic form to the polymerizable monomer is 1:0.5-1:10000.

5. The electrochromic batch of claim 1, wherein, The polymerizable monomer is selected from compounds represented by Formula 101 and / or Formula 102: wherein R1 and R4 are independently selected from hydrogen atom or methyl group; R2, R3 and R5 are independently selected from hydrogen atom, C1-C10 aliphatic alkyl group or substituted alkyl group, the substituent group of the substituted alkyl group being selected from one or more of amido, aminyl, hydroxyl, carboxyl, phosphato, phosphito, mercapto carboxyl, ether group, aldehyde group, carbonyl group, halogen and aryl group; and R6 is C1-C10 aliphatic alkyl group or substituted alkyl group, the substituent group of the substituted alkyl group being selected from one or more of amido, aminyl, hydroxyl, carboxyl, phosphato, phosphito, mercapto carboxyl, ether group, aldehyde group, carbonyl group, halogen and aryl group.

6. The electrochromic paste of claim 5, wherein, The compound represented by Formula 101 is selected from one or more of acrylamide, N-methyl methacrylamide, N,N-bis(2-hydroxyethyl) methacrylamide, 3-methyl acrylamide propionic acid, phosphoramidite monomer of acrylic acid and acrylamide-polyethylene glycol-mercapto; and the compound represented by Formula 102 is selected from one or more of N,N'-methylene bisacrylamide, N,N'-1,4-butanedioyl bis[N-[3-(phosphatoxy)propyl]-2-propenamide], N,N'-1,4-butanedioyl bis[N-(2-hydroxyethyl)-2-propenamide] and N,N'-methylene bismethacrylamide.

7. The electrochromic batch of claim 1, wherein, The polymerizable monomer further comprises a non-coordinating chelating monomer; the non-coordinating chelating monomer is selected from monomers containing one or more of olefin group, alkyne group and epoxy group, which is incapable of forming a stable chelate with the copper in ionic form during polymerization.

8. The electrochromic coating of claim 7, wherein, The monomer containing olefin group is selected from one or more of acrylate, acrylic acid, acryl, olefin group pyrrolidone, olefin group silane and vinyl group containing ionic liquid.

9. The electrochromic batch of claim 1, wherein, The metal source further comprises a second metal source in addition to the metal source of copper in ionic form; The second metal source comprises one or more of silver in ionic form, bismuth in ionic form, zinc in ionic form, gold in ionic form, aluminum in ionic form, iron in ionic form and titanium in ionic form; The molar ratio of the metal source in ionic form in the second metal source to the copper in ionic form is 100:1-1:1000.

10. The electrochromic batch of claim 1, wherein, The photoinitiator is selected from one or more of Darocur® 2959, Irgacure® TPO, Irgacure® 184, Irgacure® TPO-L, Irgacure® 1173, Irgacure® 907, Irgacure® 369, Irgacure® 1490, Irgacure® 1700, diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, triarylsiloxy ethers, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenyl ketone, a,a-dimethoxy-a-phenylacetophenone, a,a-diethoxyacetophenone, a-hydroxyalkyl phenones, a-amine alkyl phenones, aryloyl phosphine oxides, dibenzoyl phenyl phosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, Michler's ketone, thioxanthone, isopropyl thioxanthone, fluorinated titanocene diphenyls, bis(pentafluorophenyl) titanocene, and Irgacure® LAP.

11. The electrochromic batch of claim 1, wherein, The additive contains a diluent and / or a leveling agent; The diluent includes one or more of 1-ethyl-3-methyl-imidazolium bis-trifluoromethylsulfonylimide, (1-butyl-3-methylimidazolium) chloride, 1-n-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, (1-ethyl-3-methylimidazolium) chloride, (1-butyl-3-methylimidazolium) bromide, (1-ethyl-3-methylimidazolium) bromide, (1-butyl-2,3-dimethylimidazolium) chloride, 1,2-dimethyl-3-hydroxyethylimidazolium p-toluenesulfonate, 1,2-dimethyl-3-hydroxyethylimidazolium bis(trifluoromethanesulfonylimide), 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, trimethylhydroxyethylammonium bis(trifluoromethanesulfonyl)imide, N-octylpyridinium hydrogen sulfate, N-octylpyridinium perchlorate, N-hexylpyridinium bromide, trimethylhydroxyethylammonium chloride, N-methylethylpiperidinium bromide, N-methylbutylpiperidinium bis(trifluoromethylsulfonyl)imide, (N-methylbutylpyrrolidinium) chloride, (N-methylbutylpyrrolidinium) bromide, N-methylethylmethanesulfonate, methylethylmorpholinium bromide, N-methylpropylmorpholinium bis(trifluoromethylsulfonyl)imide, methyltributylphosphonium tetrafluoroborate, methyltributylphosphonium hexafluorophosphate, 1-hydroxyethyl-3-methylimidazolium bis-trifluoromethylsulfonylimide, (1-glycidoxypropyl-3-methylimidazolium) chloride, 1-glycidoxypropyl-3-methylimidazolium bis-trifluoromethylsulfonylimide, (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, dimethylsulfoxide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, and dioctyl phthalate. The leveling agent includes one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, N,N-diethylpropynylamine sulfate, polyacrylic acid, polystyrene, poly(4-sodium styrene sulfonate and maleic acid) copolymer, 1-vinylimidazole, copolymer of 1,4-butanediol glycidyl ether, and fatty acid quaternary ammonium salt.

12. A method for preparing the in-situ photocurable electrochromic paste containing copper element according to any one of claims 1-11, comprising the following steps: Mixing the metal source, polymerizable monomer, photoinitiator and additive uniformly to obtain the in-situ photocurable electrochromic paste.

13. An electrochromic device, comprising a first substrate layer, a working electrode layer, an integrated electrochromic layer, a counter electrode layer and a second substrate layer arranged in sequence. The integrated electrochromic layer is formed by photocuring the in-situ photocurable electrochromic paste containing copper element according to any one of claims 1-11.

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