Electroreflective device and preparation method therefor

Abstract

The present invention relates to the technical field of electroreflection, and provides an electroreflective device and a preparation method therefor. The electroreflective device comprises an electroreflective layer, wherein the electroreflective layer comprises a halogen-ion-free electrolyte formed by mixing a metal source and an ionic liquid, so as to solve the problem of the presence of a great number of halide anions in existing electroreflective devices affecting the stability and lifespan of the devices.

Description

An electroluminescent device and its fabrication method Technical Field

[0001] This invention relates to the field of electroluminescence technology, and in particular to an electroluminescent device and its preparation method. Background Technology

[0002] Early electroluminescent technologies all used aqueous solutions because many metal compounds can be highly or even completely ionized in aqueous solutions, resulting in electrolytes with high ionic conductivity. However, water has a high saturated vapor pressure and is prone to volatilization at room temperature, severely limiting its industrial feasibility. To dissolve the metal source in the ionic liquid system, halide anions are generally chosen as the metal source and are mixed with the ionic liquid's counterpart ions. Therefore, existing systems almost all contain halide ions.

[0003] Halogen ions, especially fluorine and chloride ions, are highly electronegative and readily form soluble ionic compounds with metals, leading to metal surface corrosion. Halogen ions and metal ions form localized corrosion cells on the metal surface, causing metal dissolution in the anodic area, resulting in the dissolution or even detachment of the working electrode layer, ultimately affecting device lifespan. Halogen ions tend to accumulate at metal surface defects (such as scratches and inclusions), forming localized high-concentration areas that trigger pitting corrosion. Furthermore, halogen ions have strong penetrability, capable of penetrating passivation films, adsorbing on the metal surface, replacing oxygen ions in the oxide film, and reacting with the metal matrix, leading to localized corrosion and ultimately affecting the lifespan of the working electrode metal layer. Summary of the Invention

[0004] In order to overcome the above-mentioned technical defects, the purpose of this invention is to provide an electroluminescent device and its preparation method, so as to solve the problem that the large number of halogen anions in existing electroluminescent devices affects the stability and lifespan of the device.

[0005] The present invention discloses an electroluminescent device, comprising an electroluminescent layer, wherein the electroluminescent layer comprises an electrolyte free of halide ions formed by mixing a metal source and an ionic liquid.

[0006] Optionally, the ionic liquid does not contain halide ions;

[0007] The metal source does not contain halide ions and is soluble in the ionic liquid to form a metal complex.

[0008] Optionally, the metal source includes a metal sulfate;

[0009] The ionic liquid includes a hydrogen sulfate ionic liquid.

[0010] Optionally, the metal sulfate includes one or more of the following: silver sulfate, copper sulfate, zinc sulfate, nickel sulfate, bismuth sulfate, and tin sulfate.

[0011] Optionally, the hydrogen sulfate ionic liquid includes one or more of the following: imidazole hydrogen sulfate and its derivatives, pyridine hydrogen sulfate and its derivatives, pyrrolidine hydrogen sulfate and its derivatives, piperidine hydrogen sulfate and its derivatives, morpholine hydrogen sulfate and its derivatives, quaternary ammonium hydrogen sulfate and its derivatives, quaternary phosphonium hydrogen sulfate and its derivatives, triazole hydrogen sulfate and its derivatives, and thiazole hydrogen sulfate compounds and their derivatives.

[0012] Optionally, the ionic liquid comprises one or more of the following: 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-propyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-octyl-3-methylimidazolium hydrogen sulfate, 1-decyl-3-methylimidazolium hydrogen sulfate, 1-methyl-3-octylimidazolium hydrogen sulfate, 1-ethyl-2,3-dimethylimidazolium hydrogen sulfate, 1-butyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hexyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hydroxyethyl-3-methylimidazolium hydrogen sulfate, 1-methoxyethyl-3-methylimidazolium hydrogen sulfate, 1-ethylpyridine hydrogen sulfate. Salts, including 1-butylpyridine hydrogen sulfate, 1-hexylpyridine hydrogen sulfate, 1-butyl-4-methylpyridine hydrogen sulfate, 1-hexyl-3-ethylpyridine hydrogen sulfate, 1-ethyl-1-methylpyrrolidine hydrogen sulfate, 1-butyl-1-methylpyrrolidine hydrogen sulfate, 1-ethyl-1-methylpiperidine hydrogen sulfate, 1-butyl-1-methylpiperidine hydrogen sulfate, 1-ethyl-1-methylmorpholine hydrogen sulfate, 1-butyl-1-methylmorpholine hydrogen sulfate, tetrabutylammonium hydrogen sulfate, trihexyltetradecylammonium hydrogen sulfate, choline hydrogen sulfate, tetrabutylphosphonium hydrogen sulfate, trihexyltetradecylphosphonium hydrogen sulfate, 1-butyl-1,2,4-triazole hydrogen sulfate, and 1-butylthiazole hydrogen sulfate.

[0013] Optionally, the electroreflective layer further includes one or more of a polymer compound, a solvent, and an additive;

[0014] The polymer compound is generated by polymerization of a polymer compound monomer with one or more of an initiator, crosslinking agent, catalyst, and polymerization inhibitor;

[0015] The polymeric compound includes one or more of the following polymers: polyacrylic acid and its derivatives, polyacrylate and its derivatives, hydroxyethyl polyacrylate and its derivatives, polyvinylpyrrolidone and its derivatives, polyurethane and its derivatives, and polyepoxy resin and its derivatives.

[0016] The solvent includes one or more of the following: γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methylpyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, sulfolane and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives.

[0017] The additives include one or more of the following: silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents, rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers, hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, and silica microspheres.

[0018] Optionally, it may also include a first substrate layer, a second substrate layer, a first electrode layer, and a second electrode layer;

[0019] The first electrode layer and the second electrode layer are located on opposite sides of the electroluminescent layer, respectively;

[0020] The first substrate layer is located on the side of the first electrode layer opposite to the electroluminescent layer;

[0021] The second substrate layer is located on the side of the second electrode layer opposite to the electroreflective layer;

[0022] At least one of the first and second base layers is made of a transparent material.

[0023] Optionally, the first substrate layer and / or the second substrate layer comprises an inorganic substrate, an organic substrate, or an inorganic-organic substrate complex;

[0024] And / or, the conductive layer of the first electrode comprises a transparent conductive film made of one or more of the following materials: indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, metallic copper, metallic silver, metallic aluminum, metallic gold, metallic platinum, 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, indium tin oxide-platinum multilayer composite material, graphene, and carbon nanotubes;

[0025] And / or, the conductive layer of the second electrode comprises a transparent conductive film made of one or more of the following materials: copper mesh, silver mesh, aluminum mesh, platinum mesh, indium tin oxide-copper multilayer composite film or mesh, indium tin oxide-silver multilayer composite film or mesh, indium tin oxide-aluminum multilayer composite film or mesh, indium tin oxide-platinum multilayer composite film or mesh, silver nanowire multilayer composite film or mesh, and platinum nanowire multilayer composite film or mesh.

[0026] This invention provides a method for preparing an electroluminescent device, comprising:

[0027] A metal source and an ionic liquid are mixed, and then mixed with a polymer compound and / or a solvent and / or an additive. A spacer is added and the mixture is stirred to obtain a mixed solution that forms an electroreflective layer.

[0028] The mixed solution is applied to the conductive layer surfaces of the first and second electrodes, and then the film is cured.

[0029] The electroluminescent device is obtained by slicing, attaching electrodes, and encapsulating.

[0030] Compared with existing technologies, the above technical solution has the following advantages:

[0031] The electroluminescent device and its preparation method provided in this application have an electrolyte in the electroluminescent layer that does not contain halide ions. Specifically, it is formed by mixing and dissolving a metal source that does not contain halide ions and an ionic liquid. Thus, no halide ions are generated during the electrolysis process, which solves the problem that the large number of halide anions in existing electroluminescent devices affects the stability and lifespan of the device, greatly improves the cycle stability of the device, and extends the number of times the device can be used and its lifespan. Attached Figure Description

[0032] Figure 1 is a schematic diagram of the device structure of an embodiment of the electroluminescent device and its preparation method according to the present invention;

[0033] Figure 2 is a flowchart of an embodiment of the electroluminescent device and its preparation method according to the present invention.

[0034] Reference numerals: 11-First substrate layer; 12-First electrode layer; 13-Electroluminescent layer; 14-Second electrode layer; 15-Second substrate layer. Detailed Implementation

[0035] The advantages of the present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments.

[0036] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings. When the following description relates to the drawings, unless otherwise indicated, the same numerals in different drawings denote the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0037] The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms “a,” “the,” and “the” as used in this disclosure and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any and all possible combinations of one or more of the associated listed items.

[0038] It should be understood that although the terms first, second, third, etc., may be used in this disclosure to describe various information, such information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another. For example, without departing from the scope of this disclosure, first information may also be referred to as second information, and similarly, second information may also be referred to as first information.

[0039] Example: This embodiment provides an electroluminescent device, as shown in Figure 1, which includes an electroluminescent layer; the electroluminescent layer includes an electrolyte that does not contain halogen ions, formed by mixing a metal source and an ionic liquid.

[0040] Understandably, in electroreflective devices, the electroreflective layer comes into contact with the electrode (metal). Free halide ions in this layer more readily form soluble ionic compounds with the metal, leading to corrosion of the metal surface and ultimately electrode dissolution and failure, significantly impacting device lifespan. The electrolyte may contain halogen-containing compounds, but these halogens exist in a combined state, not as free ions. In this case, the electrolyte may generate some halide ions during the application of the electroreflective device.

[0041] To reduce the impact of halide ions that may be generated during electrolysis on device lifespan, the electrolyte is configured to be a halide-free electrolyte, meaning that the electrolyte's composition does not contain any halogen-related substances, i.e., it does not contain either free halogens or substances existing in compound form. Specifically, a metal source and an ionic liquid that completely do not contain halogen elements (ions) are used, i.e., the ionic liquid does not contain halide ions; the metal source includes a halide-free metal source that can form a metal complex with the ionic liquid (soluble in the ionic liquid, the metal complex includes metal ions and ligands provided by the ionic liquid that can coordinate with the metal ions), so that the metal source can be mixed with the ionic liquid to prepare the electrolyte.

[0042] It is understood that the above-mentioned halogen-free electrolytes may be completely free of halogens or have extremely low halogen ion content, below a predetermined level, which may be due to the preparation environment and / or materials, and are considered as halogen-free.

[0043] Based on the above specific preferred embodiments, the metal source includes, but is not limited to, metal sulfates; the ionic liquid includes, but is not limited to, bisulfate ionic liquids.

[0044] Specifically, the metal sulfates include, but are not limited to, one or more of the following: silver sulfate, copper sulfate, zinc sulfate, nickel sulfate, bismuth sulfate, and tin sulfate.

[0045] Specifically, the hydrogen sulfate ionic liquid includes, but is not limited to, one or more of the following: imidazole hydrogen sulfate and its derivatives, pyridine hydrogen sulfate and its derivatives, pyrrolidine hydrogen sulfate and its derivatives, piperidine hydrogen sulfate and its derivatives, morpholine hydrogen sulfate and its derivatives, quaternary ammonium hydrogen sulfate and its derivatives, quaternary phosphorus hydrogen sulfate and its derivatives, triazole hydrogen sulfate and its derivatives, and thiazole hydrogen sulfate compounds and their derivatives.

[0046] Specifically, in some preferred embodiments, the ionic liquid includes, but is not limited to, one or more of the following: 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-propyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-octyl-3-methylimidazolium hydrogen sulfate, 1-decyl-3-methylimidazolium hydrogen sulfate, 1-methyl-3-octylimidazolium hydrogen sulfate, 1-ethyl-2,3-dimethylimidazolium hydrogen sulfate, 1-butyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hexyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hydroxyethyl-3-methylimidazolium hydrogen sulfate, 1-methoxyethyl-3-methylimidazolium hydrogen sulfate, 1 1-Ethylpyridine hydrogen sulfate, 1-Butylpyridine hydrogen sulfate, 1-Hexylpyridine hydrogen sulfate, 1-Butyl-4-methylpyridine hydrogen sulfate, 1-Hexyl-3-ethylpyridine hydrogen sulfate, 1-Ethyl-1-methylpyrrolidine hydrogen sulfate, 1-Butyl-1-methylpyrrolidine hydrogen sulfate, 1-Ethyl-1-methylpiperidine hydrogen sulfate, 1-Butyl-1-methylpiperidine hydrogen sulfate, 1-Ethyl-1-methylmorpholine hydrogen sulfate, 1-Butyl-1-methylmorpholine hydrogen sulfate, tetrabutylammonium hydrogen sulfate, trihexyltetradecylammonium hydrogen sulfate, etc., choline hydrogen sulfate, tetrabutylphosphonium hydrogen sulfate, trihexyltetradecylphosphonium hydrogen sulfate, 1-Butyl-1,2,4-triazole hydrogen sulfate, 1-Butylthiazole hydrogen sulfate.

[0047] Based on the above, a metal source and ionic liquid completely free of halogens are mixed and dissolved, resulting in an electrolyte that does not contain any halogen ions. No halogen ions are generated during the electrolysis process. This can greatly alleviate the problem of working electrode dissolution failure caused by halogen ions in existing electroluminescent devices, significantly improve cycle stability, and ultimately extend the number of device uses and lifespan.

[0048] In a preferred embodiment, the photoreflective layer further includes one or more of a polymer compound, a solvent, and additives; the polymer compound and / or solvent and / or additives are used to construct the framework structure of the photoreflective layer. The aforementioned metal source component and ionic liquid component are essential components, while the polymer framework component, solvent, and other additive components are optional when fabricating different types of devices.

[0049] The polymer compound is generated by the integrated (curing) polymerization of polymer compound monomers with one or more of initiators, crosslinking agents, catalysts and polymerization inhibitors inside the device.

[0050] Specifically, the polymeric compounds include, but are not limited to, one or more of the following polymers: polyacrylic acid and its derivatives, polyacrylate and its derivatives, hydroxyethyl polyacrylate and its derivatives, polyvinylpyrrolidone and its derivatives, polyurethane and its derivatives, and polyepoxy resin and its derivatives.

[0051] The solvents mentioned above include, but are not limited to, one or more of the following: γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methylpyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, sulfolane and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives.

[0052] The initiator is preferably one or more of the following: diazonium salts and their derivatives, diaryliodomonium salts and their derivatives, triarylthiomonium salts and their derivatives, alkylthiomonium salts and their derivatives, iron aromatic salts and their derivatives, sulfonyloxyketones and their derivatives, triarylsiloxanes and their derivatives, benzoin and its derivatives, benzoyl and its derivatives, alkylphenyl ketones and their derivatives, acylphosphoxides and their derivatives, benzophenones and their derivatives, 2-hydroxy-2-methylphenylacetone and its derivatives, thioxanthones and their derivatives, lithium phenyl(2,4,6-trimethylbenzoyl)phosphate and its derivatives, etc.

[0053] The crosslinking agent is preferably one or more of the following: ethylene glycol dimethacrylate and its derivatives, polyethylene glycol dimethacrylate and its derivatives, polydipentaerythritol pentaacrylate and its derivatives, ethoxylated trimethylolpropane triacrylate and its derivatives, N,N'-methylenebisacrylamide and its derivatives, etc.

[0054] The catalysts mentioned above are preferably one or more of the following: dibutyltin dilaurate and its derivatives, di(dodecylthio)dibutyltin and its derivatives, dibutyltin diacetate and its derivatives, stannous octoate and its derivatives, etc.

[0055] The aforementioned polymerization inhibitors preferably include one or more of the following: hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dibutylbiphenyl, bisphenol A, tetrachlorobenzoquinone, 1,4-naphthoquinone, aromatic nitro compounds, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, sodium sulfate, sodium sulfide, ammonium thiocyanate, and sodium dithiocarbamate.

[0056] The aforementioned additives may also include, but are not limited to, one or more of the following: antioxidants, light stabilizers, thickeners, electrolyte supplements, spacers; such as silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents, rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers, hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, silica microspheres, etc.

[0057] It is understood that the solvents and additives mentioned above are optional additions, and one or more can be added or not added depending on the actual application.

[0058] Specifically, the electroluminescent device further includes a first substrate layer, a second substrate layer, a first electrode, and a second electrode; the first electrode and the second electrode are respectively located on both sides of the reflective layer; the first substrate layer is located on the side of the first electrode layer away from the electroluminescent layer; the second substrate layer is located on the side of the second electrode layer away from the electroluminescent layer, and at least one of the first substrate layer and the second substrate layer is a transparent material (which can be completely transparent to light), that is, the first substrate layer, the first electrode layer, the electroluminescent layer, the second electrode layer, and the second substrate layer can be arranged sequentially.

[0059] Specifically, the first substrate layer and / or the second substrate layer comprises an inorganic substrate, an organic substrate, or an inorganic-organic substrate composite; the inorganic substrate may include materials such as glass or ceramics, with a thickness of 500–50,000 μm. The organic substrate includes, but is not limited to, one or more compounds such as polymethyl methacrylate and its derivatives, polyethylene terephthalate and its derivatives, polyethylene terephthalate and its derivatives, cyclic olefin copolymers and their derivatives, etc. The substrate layer thickness is 20–50,000 μm.

[0060] And / or, the conductive layer of the first electrode includes, but is not limited to, transparent conductive films made of one or more of the following materials: indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, copper, silver, aluminum, gold, platinum, 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, indium tin oxide-platinum multilayer composite material, graphene, and carbon nanotubes;

[0061] And / or, the conductive layer of the second electrode includes, but is not limited to, transparent conductive films made of one or more of the following materials: copper mesh, silver mesh, aluminum mesh, platinum mesh, indium tin oxide-copper multilayer composite film or mesh, indium tin oxide-silver multilayer composite film or mesh, indium tin oxide-aluminum multilayer composite film or mesh, indium tin oxide-platinum multilayer composite film or mesh, silver nanowire multilayer composite film or mesh, and platinum nanowire multilayer composite film or mesh.

[0062] The first electrode is used as the working electrode, and the second electrode is used as the counter electrode. The conductive layer of the second electrode can be a mesh-like or planar transparent conductive film.

[0063] This embodiment also provides a method for preparing an electroluminescent device. The method for preparing the aforementioned electroluminescent device, as shown in Figure 2, includes:

[0064] S10: Mix a metal source, an ionic liquid, a polymer monomer, and one or more of an initiator, a crosslinking agent, a solvent, an additive, and a spacer, and stir to obtain a mixed solution that forms an electroreflective layer; (the metal source and ionic liquid are used to form an electrolyte, and the polymer monomer and one or more of an initiator, a crosslinking agent, a solvent, an additive, and a spacer are used to form the molecular framework. The mixture is polymerized integrally within the device. The solvent / initiator / crosslinking agent / additive mentioned above are optional additions. The initiator, crosslinking agent, and solvent can all be selected from one or more of the above components, and other additives mentioned above or existing ones can also be introduced).

[0065] S20: The mixed solution is coated onto the conductive layer surfaces of the first electrode layer and the second electrode layer, and the film is then cured.

[0066] Specifically, the film curing process places the electroreflective layer between the first electrode layer and the second electrode layer. There are no special limitations on the thickness of the first electrode layer and the second electrode layer; they can be conventional thicknesses known to those skilled in the art.

[0067] S30: Slicing, electrode attachment, and encapsulation to obtain an electroluminescent device.

[0068] Specifically, the first substrate layer and the second substrate layer are encapsulated and integrated.

[0069] Based on the above, it is understood that this embodiment uses a halogen-free metal source and ionic liquid for mixing and dissolving, reducing a series of corrosion risks caused by halide ions and further improving device lifespan. The composition of the metal source and ionic liquid is limited; a halogen-free metal source and ionic liquid are used to obtain a halogen-free electrolyte. There are no restrictions on the polymer framework structure formed by the polymerization of one or more polymer monomers, initiators, crosslinking agents, solvents, and spacers, as long as the electrolyte is located within this polymer framework structure to form the electroreflective layer for the electroreflective device.

[0070] To demonstrate the improvement in stability and lifespan of electroluminescent devices by the halogen-free electrolyte (implemented using halogen-free ionic liquids and metal sources) of this embodiment, the following specific implementation examples are provided to fabricate corresponding devices (using the above-described fabrication process) and to perform cyclic testing on each device.

[0071] Each example includes two groups of different components (metal source, ionic liquid, polymer compound and / or solvent and / or additive) for forming a control (wherein the application group is used to prepare an electroreflective device without halide ions, and the control group is used to prepare an electroreflective device containing halide ions).

[0072] There are no particular restrictions on the source of any of the raw materials used; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0073] Implementation Example 1:

[0074] Application Group 1: 0.3g silver sulfate, 5g 1-butyl-3-methylimidazolium hydrogen sulfate, 3.5g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.1g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 0.1g vinylsiloxane;

[0075] Control group 1: 0.3g silver chloride, 5g 1-butyl-3-methylimidazolium chloride, 3.5g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.1g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 0.1g vinylsiloxane.

[0076] Device fabrication process:

[0077] S1: Mix the compounds of the corresponding mass in application group 1 or control group 1;

[0078] S2: Add 0.03g of spacers (the spacers are spherical in shape, made of polyacrylic acid resin, and have a particle size of 20μm) to the mixed solution and stir until uniform. Then, quickly coat the solution onto the surface of the PET-ITO-Au composite conductive film of the working electrode using a double-roller coating method to form an electroreflective layer.

[0079] S3: Combine the counter electrode silver mesh film with the coated PET-ITO-Au composite conductive film, and cure the slurry by irradiating it with ultraviolet light for 1 minute.

[0080] S4: Roller slicing, electrode attachment, and encapsulation yield a flexible, integrated photo-solid electroluminescent device.

[0081] The relevant cycle counts measured under the condition that the active area of ​​the device is 100mm*100mm are shown in Table 1:

[0082] In the cyclic test, the transmittance (380~2500nm) was measured according to the method in GB / T 2680-2021 "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance and Related Window Glass Parameters of Architectural Glass"; the reflectance (380~2500nm) was measured according to the method in GB / T 33234-2016 "Test Method for Reflectance of Solar Thermal Power Generation Glass Mirrors"; the dynamic change range of transmittance / reflectance in the visible and near-infrared range was the difference between the transmittance / reflectance in the tinted state and the reflectance in the untinted state in the 380~2500nm range; if the dynamic change range of transmittance / reflectance in the fading cycle of the device was less than 80% of the initial dynamic change range, it was judged as a failure.

[0083] According to Table 1 above, the devices prepared by the application group 1 (silver sulfate, imidazole hydrogen sulfate) without halogen anions have better high voltage resistance and can cycle under higher voltage conditions. The cycling stability of the devices prepared by the control group 1 (silver chloride, imidazole chloride) containing halogen anions is significantly improved at 0.9V.

[0084] Implementation Example 2:

[0085] Application Group 2: 0.2g silver sulfate, 6g tetrabutylammonium hydrogen sulfate, 3.2g hydroxyethyl acrylate, 0.5g glyceryl triacrylate, 0.1g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide;

[0086] Control group 2: 0.2g silver chloride, 6g tetrabutylammonium chloride, 3.2g hydroxyethyl acrylate, 0.5g glyceryl triacrylate, and 0.1g phenyl (2,4,6-trimethylbenzoyl)phosphine oxide.

[0087] The device fabrication process is described in steps S1-S4 of Example 1.

[0088] The relevant cycle counts measured under the condition that the active area of ​​the device is 100mm*100mm are shown in Table 2:

[0089] As shown in Table 2, the devices prepared by the halogen-free anion system in Group 2 (silver sulfate, tetrabutylammonium hydrogen sulfate) have better high-voltage resistance and can cycle under higher voltage conditions. At 0.9V, the devices prepared by the halogen-containing control group 2 (silver chloride, tetrabutylammonium chloride) have significantly improved cycle stability.

[0090] Implementation Example 3:

[0091] Application Group 3: 0.2g silver sulfate, 0.1g nickel sulfate, 5g 1-butyl-3-methylimidazolium hydrogen sulfate, 3.5g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.1g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 0.1g vinylsiloxane;

[0092] Control group 3: 0.2g silver chloride, 0.1g nickel chloride, 5g 1-butyl-3-methylimidazolium chloride, 3.5g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.1g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 0.1g vinylsiloxane.

[0093] The device fabrication process is as described in the above implementation examples 1S1-S4.

[0094] The relevant cycle counts measured under the condition that the active area of ​​the device is 100mm*100mm are shown in Table 3:

[0095] As shown in Table 3, the devices prepared by the halogen-free anion system in Group 3 (silver sulfate, nickel sulfate, imidazole hydrogen sulfate) have better high-voltage resistance and can cycle under higher voltage conditions. At 0.9V, the devices prepared by the control group 3 (silver chloride, silver chloride, imidazole chloride) containing halogen anions have significantly improved cycle stability.

[0096] Based on the various application groups and control groups in the above implementation examples 1-3, the anions in each application group and control group are different, and the number of cycles to achieve the same transmittance and reflectance under cyclic testing is significantly different. Moreover, the application group (halogen-free system) is significantly better than the control group (halogen system). This verifies that the application of the above-formed halogen-free electrolyte in the device greatly alleviates the problem of working electrode dissolution failure caused by halogen ions in the existing electroluminescent devices, significantly improves cycle stability, and ultimately extends the number of device uses and lifespan.

[0097] It should be noted that the embodiments of the present invention have better implementability and are not intended to limit the present invention in any way. Any person skilled in the art may use the above-disclosed technical content to change or modify it into equivalent effective embodiments. However, any modifications or equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. An electroluminescent device, characterized in that: It includes an electroreflective layer comprising an electrolyte that does not contain halide ions, formed by mixing a metal source and an ionic liquid.

2. The electroluminescent device according to claim 1, characterized in that: The ionic liquid does not contain halide ions; The metal source does not contain halide ions and forms a metal complex with the ionic liquid.

3. The electroluminescent device according to claim 1, characterized in that: The metal source includes metal sulfates; The ionic liquid includes a hydrogen sulfate ionic liquid.

4. The electroluminescent device according to claim 3, characterized in that: The metal sulfates include one or more of the following: silver sulfate, copper sulfate, zinc sulfate, nickel sulfate, bismuth sulfate, and tin sulfate.

5. The electroluminescent device according to claim 3, characterized in that: The hydrogen sulfate ionic liquid includes one or more of the following: imidazole hydrogen sulfate and its derivatives, pyridine hydrogen sulfate and its derivatives, pyrrolidine hydrogen sulfate and its derivatives, piperidine hydrogen sulfate and its derivatives, morpholine hydrogen sulfate and its derivatives, quaternary ammonium hydrogen sulfate and its derivatives, quaternary phosphonium hydrogen sulfate and its derivatives, triazole hydrogen sulfate and its derivatives, and thiazole hydrogen sulfate compounds and their derivatives.

6. The electroluminescent device according to any one of claims 1 to 5, characterized in that: The ionic liquid comprises one or more of the following: 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-propyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-octyl-3-methylimidazolium hydrogen sulfate, 1-decyl-3-methylimidazolium hydrogen sulfate, 1-methyl-3-octylimidazolium hydrogen sulfate, 1-ethyl-2,3-dimethylimidazolium hydrogen sulfate, 1-butyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hexyl-2,3-dimethylimidazolium hydrogen sulfate, 1-hydroxyethyl-3-methylimidazolium hydrogen sulfate, 1-methoxyethyl-3-methylimidazolium hydrogen sulfate, and 1-ethylpyridine hydrogen sulfate. 1-Butylpyridine hydrogen sulfate, 1-hexylpyridine hydrogen sulfate, 1-butyl-4-methylpyridine hydrogen sulfate, 1-hexyl-3-ethylpyridine hydrogen sulfate, 1-ethyl-1-methylpyrrolidine hydrogen sulfate, 1-butyl-1-methylpyrrolidine hydrogen sulfate, 1-ethyl-1-methylpiperidine hydrogen sulfate, 1-butyl-1-methylpiperidine hydrogen sulfate, 1-ethyl-1-methylmorpholine hydrogen sulfate, 1-butyl-1-methylmorpholine hydrogen sulfate, tetrabutylammonium hydrogen sulfate, trihexyltetradecylammonium hydrogen sulfate, etc., choline hydrogen sulfate, tetrabutylphosphonium hydrogen sulfate, trihexyltetradecylphosphonium hydrogen sulfate, 1-butyl-1,2,4-triazole hydrogen sulfate, 1-butylthiazole hydrogen sulfate.

7. The electroluminescent device according to claim 1, characterized in that: The electroreflective layer further includes one or more of a polymer compound, a solvent, and an additive; The polymeric compounds include one or more of the following: polyacrylic acid and its derivatives, polyacrylate and its derivatives, hydroxyethyl polyacrylate and its derivatives, polyvinylpyrrolidone and its derivatives, polyurethane and its derivatives, and polyepoxy resin and its derivatives. The solvent includes one or more of the following: γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methylpyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, sulfolane and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives. The additives include one or more of the following: silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents, rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers, hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, and silica microspheres.

8. The electroluminescent device according to claim 1, characterized in that: It also includes a first substrate layer, a second substrate layer, a first electrode layer, and a second electrode layer; The first electrode layer and the second electrode layer are located on opposite sides of the electroluminescent layer, respectively; The first substrate layer is located on the side of the first electrode layer opposite to the electroluminescent layer; The second substrate layer is located on the side of the second electrode layer opposite to the electroreflective layer; At least one of the first and second base layers is made of a transparent material.

9. The electroluminescent device according to claim 8, characterized in that: The first substrate layer and / or the second substrate layer include an inorganic substrate, an organic substrate, or an inorganic-organic substrate complex; And / or, the conductive layer of the first electrode comprises a transparent conductive film made of one or more of the following materials: indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, metallic copper, metallic silver, metallic aluminum, metallic gold, metallic platinum, 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, indium tin oxide-platinum multilayer composite material, graphene, and carbon nanotubes; And / or, the conductive layer of the second electrode comprises a transparent conductive film made of one or more of the following materials: copper mesh, silver mesh, aluminum mesh, platinum mesh, indium tin oxide-copper multilayer composite film or mesh, indium tin oxide-silver multilayer composite film or mesh, indium tin oxide-aluminum multilayer composite film or mesh, indium tin oxide-platinum multilayer composite film or mesh, silver nanowire multilayer composite film or mesh, and platinum nanowire multilayer composite film or mesh.

10. A method for preparing an electroluminescent device, characterized in that, The preparation of the electroluminescent device according to any one of claims 1-9 comprises: A mixed solution is prepared by mixing a metal source, an ionic liquid, a polymer monomer, and one or more of an initiator, a crosslinking agent, a solvent, an additive, and a spacer, and stirring the mixture to obtain a mixed solution that forms an electroreflective layer. The mixed solution is applied to the conductive layer surfaces of the first and second electrodes, and then the film is cured. The electroluminescent device is obtained by slicing, attaching electrodes, and encapsulating.

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