Integrated electro-reflective device and preparation method thereof

Abstract

The invention relates to the technical field of electro-reflective devices, in particular to an integrated electro-reflective device and a preparation method thereof, and the integrated electro-reflective device comprises an integrated electro-reflective layer; the integrated electro-reflective layer comprises an ionic liquid; the ionic liquid comprises a long-chain alkyl compound, and the number of carbon atoms of the long-chain alkyl compound is 6 or more. According to the invention, the long-chain alkyl compound is used as the ionic liquid to prepare the electro-reflective device, so that the water and oxygen resistance of the device is improved, the electrolyte viscosity is adjusted by a longer alkyl chain, and the formation of smaller, denser and more uniformly distributed electro-deposited metal nanoparticles is facilitated; the electrodeposited nano-particle film has the advantages of higher switching speed, excellent cycle durability, small particle size and uniform electrodeposited nano-particle film. And even under the condition of simple packaging, a good electro-deposition effect and excellent cycling stability of the device can be realized, so that the performance of the device can be accurately regulated and controlled through a circuit.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrochromic devices, in particular to an integrated electrochromic device and a preparation method thereof. BACKGROUND

[0002] An electrochromic device generally refers to a photoelectric device that changes the reflectivity of light by applying a certain voltage. The main implementation method is through reversible electrodeposition technology of metal. When the working electrode is given a certain electrochemical control (changing the voltage or passing a certain intensity of current through the system), the metal cations in the device system will be reduced to metal elements on the main reaction plate and form a metal film attached to the working electrode. At this time, the state is called the reflective state of the electrochromic device. Based on the characteristics of the metal itself, the incident sunlight will be reflected back by the metal film, and will not enter the room or the car interior. It has unique advantages such as simple structure, low energy consumption, and multi-color state control, and shows great application potential in intelligent windows, heat management, information display and other fields.

[0003] The electrochromic device is often used outdoors. In order to improve the water and oxygen resistance of the device, improve its cycle stability, and prolong its service life, the device often needs to be packaged to achieve water and oxygen resistance barrier performance, which also increases the production and research and development cost.

[0004] For example, the existing electrochromic device needs to be packaged with a glass substrate with very good sealing performance to avoid problems such as unstable current control, short cycle life, and the like caused by water absorption and oxidation. However, this also limits its application field and industrialized mass production. In some cases where packaging requirements cannot be met, such as in flexible devices, due to the lack of glass sealing, the reversible electrodeposition system inside will have problems such as unstable current and short cycle life due to water absorption and oxidation.

[0005] The addition of water absorption agents and antioxidants to the active layer formula can improve the water and oxygen resistance of the device. However, the selected water and oxygen resistance agents may not be compatible with the formula system, and the selection difficulty is very high. Moreover, the introduction of water and oxygen resistance agents will increase the difficulty of circuit control.

[0006] How to reduce the influence of external factors (temperature, humidity, oxygen) on the electrochromic device without introducing water and oxygen resistance agents and improve its cycle stability is a problem that needs to be solved at present. SUMMARY

[0007] Therefore, the technical problem to be solved by the present application is to provide an integrated electrochromic device and a preparation method thereof. The prepared device has high cycle stability.

[0008] To achieve the above object, the application provides an integrated electroreflective device, comprising an integrated electroreflective layer; the integrated electroreflective layer comprises an ionic liquid.

[0009] The ionic liquid comprises a long-chain alkyl compound, and the number of carbon atoms of the long-chain alkyl compound is 6 or more.

[0010] The application improves the water-oxygen resistance of the integrated electroreflective layer by increasing the carbon chain length of the molecular structure of the ionic liquid, thereby improving the reflection performance and cycle stability of the device, reducing the packaging difficulty of the device, and making it easier to realize industrialization.

[0011] Preferably, the number of carbon atoms of the long-chain alkyl compound is 6-20, and in some specific embodiments of the application, the number of carbon atoms of the long-chain alkyl compound is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, or a range value above or below any of the above-mentioned values.

[0012] Preferably, the long-chain alkyl compound is selected from one or more of alkyl imidazole salt, alkyl pyridine salt, alkyl pyrrole salt, alkyl quaternary ammonium salt, alkyl quaternary phosphonium salt, fluoroalkyl imidazole salt, fluoroalkyl pyridine salt, fluoroalkyl pyrrole salt, fluoroalkyl quaternary ammonium salt, and fluoroalkyl quaternary phosphonium salt.

[0013] In some specific embodiments of the application, the long-chain alkyl compound is selected from one or more of 1-C6-C20 alkyl-3-methyl imidazole salt, 1-vinyl-3-C6-C20 alkyl imidazole salt, and N-C6-C20 alkyl pyridine salt.

[0014] The anion of the above-mentioned long-chain alkyl compound includes but is not limited to halogen ion, tetrafluoroborate ion, hexafluorophosphate ion, fluorosulfonylimide ion, trifluoromethanesulfonylimide ion, and bistrifluoromethanesulfonylimide ion.

[0015] In some specific embodiments of the application, the long-chain alkyl compound is selected from one or more of 1-dodecyl-3-methyl imidazole chloride, 1-vinyl-3-hexyl imidazole trifluoromethanesulfonylimide salt, 1-vinyl-3-dodecyl imidazole trifluoromethanesulfonylimide salt, N-dodecyl pyridine hexafluorophosphate salt, N-eicosyl pyridine hexafluorophosphate salt, and 1-dodecyl-3-methyl imidazole trifluoromethanesulfonylimide salt.

[0016] The mass content of the ionic liquid in the integrated electroreflective layer is preferably 20%-90%.

[0017] The other components of the integrated electroreflective layer are not particularly limited, and can be electroreflective layer materials suitable for integrated electroreflective devices known to those skilled in the art.

[0018] Preferably, the integrated electroreflective layer further comprises a metal source, and one or more of a polymer compound, a solvent, and an additive.

[0019] The metal source is an essential component, and is preferably one or more of silver chloride, silver bromide, silver iodide, silver acetate, silver nitrate, silver perchlorate, silver perbromate, silver periodate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver triflate, silver bistrifluoromethanesulfonimide, copper fluoride, copper chloride, copper bromide, copper iodide, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, aurous chloride, aurous sulfide, nickel chloride, nickel sulfate, cobalt chloride, platinum chloride, and other metal compound materials; in some embodiments of the present application, the metal source is silver nitrate, silver bromide, silver bistrifluoromethanesulfonimide, or copper chloride.

[0020] The mass content of the metal source in the integrated electroreflective layer is preferably 1% to 30%.

[0021] Preferably, the integrated electroreflective layer further comprises one or more of a polymer compound, a solvent, and an additive, which are non-essential components and can be freely selected according to the type of the device.

[0022] The polymer compound preferably comprises one or more of the following polymers: polyacrylic acid and its derivatives, polyacrylate and its derivatives, polyhydroxyethyl acrylate and its derivatives, polyvinylpyrrolidone and its derivatives, polyurethane and its derivatives, polyepoxy resin and its derivatives, and copolymers of the above polymers.

[0023] In the present application, the polymer compound is integrated and polymerized during the preparation of the device.

[0024] Preferably, the polymer compound is generated by integrated polymerization of one or more of the following polymer monomers, initiators, cross-linking agents, catalysts, and polymerization inhibitors inside the device.

[0025] Preferably, the polymerizing monomer includes one or more of the following: acrylic acid and its derivatives, acrylates and their derivatives, hydroxyethyl acrylate and its derivatives, N-vinyl-2-pyrrolidone and its derivatives, diphenylmethane diisocyanate and its derivatives, toluene diisocyanate and its derivatives, isophorone diisocyanate and its derivatives, dicyclohexylmethane diisocyanate and its derivatives, hexamethylene diisocyanate and its derivatives, L-lysine diisocyanate and its derivatives, polyols and their derivatives, polyamines and their derivatives, phenyl dioxide epoxy resin and its derivatives, glycidyl ether and its derivatives.

[0026] The initiator preferably includes one or more of the following: diazonium salts and their derivatives, diaryliodomonium salts and their derivatives, triarylthiomonium salts and their derivatives, alkylthiomonium salts and their derivatives, iron aromatic salts and their derivatives, sulfonyloxyketones and their derivatives, triarylsiloxanes and their derivatives, benzoin and its derivatives, benzoyl and its derivatives, alkylphenyl ketones and their derivatives, acylphosphoxides and their derivatives, benzophenones and their derivatives, 2-hydroxy-2-methylphenylacetone and its derivatives, thioxanthones and their derivatives, and lithium phenyl(2,4,6-trimethylbenzoyl)phosphate and its derivatives.

[0027] The crosslinking agent preferably includes one or more of the following: ethylene glycol dimethacrylate and its derivatives, polyethylene glycol dimethacrylate and its derivatives, polydipentaerythritol pentaacrylate and its derivatives, ethoxylated trimethylolpropane triacrylate and its derivatives, N,N'-methylenebisacrylamide and its derivatives.

[0028] The catalyst preferably includes one or more of the following: dibutyltin dilaurate and its derivatives, di(dodecylthio)dibutyltin and its derivatives, dibutyltin diacetate and its derivatives, stannous octoate and its derivatives.

[0029] The polymerization inhibitor preferably includes one or more of the following: hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, 4,4'-dibutylbiphenyl, bisphenol A, tetrachlorobenzoquinone, 1,4-naphthoquinone, aromatic nitro compounds, p-toluidine, diphenylamine, benzidine, p-phenylenediamine, N-nitrosodiphenylamine, 1,1-diphenyl-2-trinitrophenylhydrazine, sodium sulfate, sodium sulfide, ammonium thiocyanate, and sodium dithiocarbamate.

[0030] The polymer compound is preferably present in the integrated electroreflective layer at a mass content of 5% to 50%.

[0031] The aforementioned polymer compounds serve to support the mechanical structure of the entire electroreflective layer, ensure compatibility with active materials and ionic liquids to prevent precipitation, and provide a favorable environment for ion migration.

[0032] The solvent is preferably 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.

[0033] The solvent content in the integrated electroreflective layer is preferably 0% to 20% by mass.

[0034] The role of the solvent mentioned above is to dissolve the components so that they do not precipitate, while providing a good environment for ion migration.

[0035] When the integrated electroreflective layer of the present invention is a solid system, no solvent needs to be added to the system.

[0036] The additives preferably include one or more of the following: coupling agents, antioxidants, light stabilizers, thickeners, electrolyte supplements, spacers, etc.

[0037] The present invention does not impose any particular limitation on the types of coupling agents, antioxidants, light stabilizers, thickeners, electrolyte supplements, and spacers mentioned above, and can be any applicable types known to those skilled in the art.

[0038] Preferably, the additives include one or more of the following: silane coupling agents, titanate coupling agents, zirconate coupling agents, aluminate coupling agents, bimetallic coupling agents (including but not limited to aluminum-zirconate, aluminum-titanium composite coupling agents, etc.), rare earth coupling agents, phosphorus-containing coupling agents, boron-containing coupling agents, hindered amine light stabilizers (HALS), hindered phenolic antioxidants, methylene blue, ferrocene and its derivatives, acrylate polyols, sodium polyacrylate, polypentaerythritol sodium acrylate, sodium alginate, carboxymethyl cellulose, polyglycerol, lithium nitrate, polystyrene microspheres, polyacrylate microspheres, and silica microspheres.

[0039] The mass fraction of the above-mentioned additives in the integrated electroreflective layer is preferably 0% to 5%.

[0040] The additives mentioned above enhance the interfacial bonding between the electroreflective layer and the electrode layer, increase the electroreflective layer's resistance to external oxygen and ambient light, and enhance conductivity and structural support.

[0041] In preparing the integrated electroreflective layer, this invention employs in-situ polymerization of monomers. A slurry or solution containing the raw materials for the integrated electroreflective layer is first prepared, and then cured in situ within the device to form a gel-like or solid integrated electroreflective layer. Therefore, no solvent is required, avoiding problems such as bubbling, wrinkling, cracking of the active layer, and performance degradation caused by solvent evaporation during later device use.

[0042] In some specific embodiments of the present invention, the paste forming the integrated electroreflective layer includes silver nitrate, 1-dodecyl-3-methylimidazolium chloride, hydroxyethyl acrylate, ethylene glycol diacrylate, lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, propylene carbonate, vinylsiloxane, and polyglycerol.

[0043] In some specific embodiments of the present invention, the paste forming the integrated electroreflective layer includes silver bromide, 1-vinyl-3-dodecylimidazolium trifluoromethanesulfonylimide salt, acrylic acid, N,N'-methylenebisacrylamide, 2-hydroxy-2-methylphenylacetone, hydroquinone, and γ-glycidoxypropyltrimethoxysilane.

[0044] In some specific embodiments of the present invention, the slurry forming the integrated electroreflective layer includes silver bis(trifluoromethanesulfonyl)imide, N-dodecylpyridine hexafluorophosphate, ethylene glycol monoethyl ether, aminosiloxane, acrylate polyol, isophorone diisocyanate, dibutyltin diacetate, and lithium nitrate.

[0045] In some specific embodiments of the present invention, the slurry forming the integrated electroreflective layer includes copper chloride, 1-dodecyl-3-methylimidazolium chloride, polyethylene glycol 1000, and lithium nitrate.

[0046] Figure 1 This is a schematic diagram of the integrated electroluminescent device provided by the present invention.

[0047] Preferably, the integrated electroluminescent device provided by the present invention comprises, in sequence:

[0048] First base layer 1, working electrode layer 2, integrated electroreflective layer 3, counter electrode layer 4, and second base layer 5.

[0049] When electroplated metal cations undergo a reduction reaction on the working electrode layer 2 to form a metal thin film, the metal plate, metal mesh, or foil on the counter electrode layer 4 undergoes an oxidation reaction, turning into metal cations that are released into the integrated electroreflective layer 3. When the voltage polarity is reversed, the metal thin film formed on the working electrode layer 2 is oxidized back into metal cations, leaving the working electrode layer 2 and redissolving into the integrated electroreflective layer 3. The counter electrode layer 4 also undergoes a corresponding reduction reaction. At this point, the electroreflective device completes its transition to a non-reflective state.

[0050] The present invention does not have any particular limitation on the material of the first substrate layer and the second substrate layer, and can be any substrate material known to those skilled in the art. Preferably, it is an inorganic substrate, an organic substrate, or an inorganic-organic composite substrate.

[0051] The inorganic substrate material is preferably glass, diamond, ceramic, or similar materials. Its thickness is preferably 500–50000 μm.

[0052] The organic substrate material is preferably one or more of the following: polymethyl methacrylate and its derivatives, polyethylene terephthalate and its derivatives, polyethylene terephthalate and its derivatives, cyclic olefin copolymers and their derivatives, cellulose triacetate and its derivatives, polyethersulfone resins and their derivatives, polyimide and its derivatives, polycarbonate and its derivatives, polyethylene, polypropylene, polyvinyl chloride, thermoplastic polyurethane, polysulfone, and acrylonitrile-butadiene-styrene terpolymers. Its thickness is preferably 20–50,000 μm.

[0053] In this invention, at least one side of the first base layer and the second base layer is a transparent material, and the other side can be a transparent or non-transparent material.

[0054] Preferably, the conductive layer material of the working electrode layer is selected from one or more of the following materials: indium tin oxide (ITO), zinc aluminum oxide (AZO), fluorine-doped tin oxide (FTO), copper nanowires, silver nanowires, aluminum nanowires, copper mesh, silver mesh, aluminum mesh, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, graphene, carbon nanotubes, and silver nanopaste.

[0055] In this invention, the conductive layer material of the counter electrode is selected from a transparent conductive metal electrode.

[0056] Preferably, the conductive layer material of the counter electrode layer is selected from one or more of the following: copper nanowires, silver nanowires, aluminum nanowires, copper mesh, silver mesh, aluminum mesh, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, and silver nanopaste.

[0057] This invention uses a transparent conductive metal electrode as the counter electrode, which can play a role in electron transport and participate in redox while ensuring the transparency of the device. Based on this, this invention has prepared an integrated transparent electroluminescent device.

[0058] The present invention does not specifically limit the preparation methods of the above-mentioned counter electrode and working electrode, which can be commercially available electrodes or electrodes prepared according to methods well known to those skilled in the art. These methods include, but are not limited to, forming conductive films or conductive plates on the surface of flexible or rigid substrates by means of magnetron sputtering, screen printing, ion beam evaporation, or chemical deposition.

[0059] The present invention does not impose any special limitation on the thickness of the working electrode layer and the counter electrode layer, and the thickness can be a conventional thickness known to those skilled in the art.

[0060] Preferably, the thickness of the working electrode layer is 1–20 nm, more preferably 3–10 nm.

[0061] Preferably, the thickness of the mesh electrode layer is 1–15 μm, more preferably 8–10 μm, and the porosity is 20%–90%, more preferably 60%–70%. The thickness of the film electrode layer is 1–20 nm, more preferably 3–10 nm.

[0062] The thickness of the integrated electroluminescent layer is preferably 5–3000 μm, more preferably 20–500 μm. In some specific embodiments of the present invention, the thickness of the integrated electroluminescent layer is 50 μm, 100 μm, or 200 μm.

[0063] This invention also provides a method for preparing the above-mentioned integrated electroluminescent device, comprising the following steps:

[0064] S1) Apply the integrated electroreflective layer solution or slurry to the surface of the counter electrode or working electrode, seal the film and cure the solution or slurry;

[0065] S2) Laser slicing, electrode attachment, and encapsulation yield an integrated electroluminescent device;

[0066] Or it may include the following steps:

[0067] S11) Drill pre-drilled holes on a rigid conductive substrate, attach the working electrode plate and the counter electrode plate face to face, and use spacers to control the plate spacing to form a hollow device shell.

[0068] S22) Inject the integrated electroreflective layer solution or slurry into the hollow device shell through the aforementioned pre-formed holes;

[0069] S33) Dispensing and sealing to solidify the solution or slurry, resulting in an integrated electroluminescent device.

[0070] Compared with the prior art, the present invention provides an integrated electroluminescent device, including an integrated electroluminescent layer; the integrated electroluminescent layer includes an ionic liquid; the ionic liquid includes a long-chain alkyl compound, wherein the long-chain alkyl compound has 6 or more carbon atoms.

[0071] This invention utilizes long-chain alkyl compounds as ionic liquids to fabricate electroreflective devices, improving the devices' resistance to water and oxygen. The longer alkyl chains adjust the electrolyte viscosity, facilitating the formation of smaller, denser, and more uniformly distributed electrodeposited metal nanoparticles. This results in faster switching speeds, excellent cycle durability, and small-particle-size, uniform electrodeposited nanoparticle films. Even with simple packaging, good electrodeposition effects and superior cycle stability can be achieved, which also allows for precise control of device performance through circuitry. Attached Figure Description

[0072] Figure 1 This is a schematic diagram of the integrated electroluminescent device provided by the present invention. Detailed Implementation

[0073] To further illustrate the present invention, the integrated electroluminescent device and its fabrication method provided by the present invention are described in detail below with reference to embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims.

[0074] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0075] Example 1

[0076] S1 is made by mixing 0.5g silver nitrate, 5g 1-dodecyl-3-methylimidazolium chloride, 4g hydroxyethyl acrylate, 1g ethylene glycol diacrylate, 0.01g lithium phenyl (2,4,6-trimethylbenzoyl)phosphate, 5g propylene carbonate, 0.1g vinylsiloxane, and 1g polyglycerol 10.

[0077] S2 adds 0.03g of spacers (spherical in shape, made of polyacrylic acid resin, with a particle size of 100μm) to the mixed solution, stirs until uniform, and then quickly coats the working electrode PET-ITO-Au composite conductive film using a two-roller coating method.

[0078] S3 combines the counter electrode silver mesh film with the coated PET-ITO-Au composite conductive film and cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0079] S4 roller slicing, electrode attachment, and encapsulation yield a flexible photo-solid integrated gel electroluminescent device with an active area of ​​100mm*100mm and an electroluminescent layer thickness of 100μm.

[0080] Comparative Example 1

[0081] Replace the 1-dodecyl-3-methylimidazolium chloride in step S1 of Example 1 with 1-butyl-3-methylimidazolium chloride, and otherwise remain the same as in Example 1.

[0082] The current and reflectance variations in the visible and infrared ranges (380–2500 nm) of devices prepared using ionic liquids with different carbon chains in Example 1 and Comparative Example 1 during the cycling process were measured, as shown in Table 1. The reflectance was determined according to the method in GB / T 33234-2016 "Test Method for Reflectance of Photothermal Power Generation Glass Mirrors". The device cycling steps were as follows: 1. Charge calculation: The device was first colored under a voltage of -1V, and the cycle stopped when the reflectance change reached 25%, recorded as Q. 2. Cyclic coloring stage: The voltage was -1V, and the cycle stopped when the charge integrated to Q. 3. Cyclic rest stage: The voltage was 0V, lasting 30 seconds. 4. Cyclic fading stage: The voltage was +0.3V, and the cycle stopped when the charge integrated to Q. In Table 1, the current is the current of the device after the corresponding number of cycles, colored for 30 seconds under a voltage of -1V. The results show that adjusting the carbon chain length can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0083] Table 1

[0084]

[0085] The coloring and fading times were determined as follows: the electroluminescent devices were placed in a UV-Vis spectrometer, and the maximum and minimum transmittance values ​​were measured at 550 nm. The time taken for the transmittance to change from the maximum to the minimum was recorded as the coloring time, and the time taken for the transmittance to change from the minimum to the maximum was recorded as the fading time. The coloring and fading times for different cycles are shown in Table 2.

[0086] Table 2

[0087]

[0088]

[0089] Table 2 shows that when the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring and fading times of devices prepared with ionic liquids of different chain lengths vary during cycling. The coloring and fading times of long-chain ionic liquids are more stable, which reduces the difficulty of circuit control and packaging, laying the foundation for large-scale industrial production.

[0090] Example 2

[0091] S1 is a mixture of 0.5g silver bromide, 6g 1-vinyl-3-hexylimidazolium trifluoromethanesulfonylimide salt, 5g acrylic acid, 1g N,N'-methylenebisacrylamide, 0.01g 2-hydroxy-2-methylphenylacetone, 0.005g hydroquinone, and 0.1g γ-glycidoxypropyltrimethoxysilane.

[0092] S2 adds 0.04g of spacers (the spacers are spherical in shape, made of silicon dioxide, and have a particle size of 100μm) to the mixed solution, stirs it evenly, and then quickly coats it onto the counter electrode nano-silver film using a double roller coating method.

[0093] S3 combines the working electrode PET-ITO-Pt composite conductive film with the counter electrode nano silver film, and then cures the slurry by irradiating it with ultraviolet light for 1 minute.

[0094] S4 molding, slicing, electrode attachment, and encapsulation yield a flexible, integrated photo-solid electroreflective device with an active area of ​​100mm*100mm and an electroreflective layer thickness of 100μm.

[0095] Comparative Example 2

[0096] Replace the 1-vinyl-3-hexylimidazolium trifluoromethanesulfonylimide salt in step S1 of Example 2 with 1-vinyl-3-butylimidazolium trifluoromethanesulfonylimide salt, otherwise the same as in Example 2.

[0097] The differences in current and reflectance in the visible and infrared ranges (380–2500 nm) during cycling of devices prepared with different carbon chain ionic liquids are shown in Table 3 below. The test method is the same as in Example 1. Table 3 shows that adjusting the length of the carbon chain can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0098] Table 3

[0099]

[0100]

[0101] The coloring and fading times of ionic liquids with different chain lengths are shown in Table 4 below. The test method is the same as that in Example 1.

[0102] Table 4

[0103]

[0104] Table 4 shows that when the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring time and fading time of devices prepared with ionic liquids of different chain lengths are not the same during the cycling process. The time of long-chain ionic liquids is more stable, which also reduces the difficulty of circuit control and packaging.

[0105] Example 3

[0106] S1 is a mixture of 0.6g bis(trifluoromethanesulfonyl)imide silver, 5g N-eicosylpyridine hexafluorophosphate, 5g ethylene glycol monoethyl ether, 0.1g aminosiloxane, 2g acrylate polyol, 0.1g isophorone diisocyanate, 0.01g dibutyltin diacetate, and 0.2g lithium nitrate.

[0107] S2 adds 0.03g of spacers (spherical in shape, made of polystyrene resin, with a particle size of 100μm) to the mixed solution, stirs until homogeneous, and then rapidly coats the working electrode PET-ITO-Pt composite conductive film using a two-roller coating method.

[0108] S3 combines the working electrode PET-ITO-Pt composite conductive film with the counter electrode PET-ITO-Ag composite conductive film, and accelerates the curing of the electroluminescent paste by heating.

[0109] S4 laser slicing, electrode attachment, and encapsulation yielded a thermosetting flexible integrated gel electroreflective device with an active area of ​​100mm*100mm and an electroreflective layer thickness of 100μm.

[0110] Comparative Example 3

[0111] Replace N-eicosylpyridine hexafluorophosphate in step S1 of Example 3 with N-butylpyridine hexafluorophosphate, otherwise the same as in Example 3.

[0112] Table 5 shows the reflectance difference and current variation data of devices prepared with different carbon chain ionic liquids in the visible and near-infrared range (380–2500 nm) for both colored and uncolored states. The testing method was the same as in Example 1. Table 5 shows that adjusting the length of the carbon chain can reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0113] Table 5

[0114]

[0115] When the device is made using a PET substrate with poor water and oxygen barrier properties, the coloring and fading times of ionic liquids with different chain lengths are shown in Table 6 below. The test method is the same as in Example 1.

[0116] Table 6

[0117]

[0118] Table 6 shows that, under simple packaging conditions, the coloring and fading times of devices prepared with ionic liquids of different chain lengths vary during cycling. The time of long-chain ionic liquids is more stable, which also reduces the difficulty of circuit control and packaging.

[0119] Example 4

[0120] S1 uses a laser to cut injection holes in ITO glass, applies adhesive, and attaches the working electrode ITO and the counter electrode conductive silver glass face to face. Spacers (spherical in shape, made of polyacrylic acid resin, with a particle size of 200 μm) or spacer strips (strip-shaped, with a thickness of 200 μm) are used to control the distance between the two electrode surfaces to 200 μm.

[0121] S2 mixes 0.5g of bis(trifluoromethanesulfonyl)imide silver, 5g of 1-dodecyl-3-methylimidazolium trifluoromethanesulfonylimide salt, 5g of hydroxyethyl methacrylate, 2g of polyethylene glycol 1000, and 0.2g of lithium nitrate.

[0122] S3 injects the solution into the device through a pre-made hole in the conductive glass;

[0123] S4 dispensing and sealing, UV curing, to obtain an integrated photo-curable rigid gel electroreflective device with an active area of ​​100mm*100mm and a thickness of 100μm for the electroreflective layer.

[0124] Comparative Example 4

[0125] Replace the 1-dodecyl-3-methylimidazolium chloride in step S2 of Example 4 with 1-butyl-3-methylimidazolium trifluoromethanesulfonylimide salt, otherwise the same as in Example 4.

[0126] Table 7 below shows the changes in current and reflectance difference in the visible and near-infrared range (380–2500 nm) for the colored and uncolored states of the devices prepared in Example 4 and Comparative Example 4. The testing method is the same as in Example 1. Table 7 shows that when using a rigid substrate with strong resistance to water and oxygen, adjusting the length of the carbon chain can also reduce current fluctuations and result in a more stable reflectance difference during cycling.

[0127] Table 7

[0128]

[0129] The coloring and fading times of devices prepared with ionic liquids of different chain lengths are shown in Table 8 below. The test methods are the same as those in Example 1.

[0130] Table 8

[0131]

[0132] Table 8 shows that when using a rigid substrate with strong resistance to water and oxygen, the coloring and fading times of ionic liquid devices with different chain lengths vary during cycling. The coloring and fading times of long-chain ionic liquids are more stable, which reduces the difficulty of circuit control and packaging.

[0133] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. An integrated electrochromic device, characterized by The integrated electrochromic reflective layer comprises an ionic liquid. The ionic liquid comprises a long-chain alkyl compound with a carbon atom number of 6 or more.

2. The integrated electrochromic device of claim 1, wherein, The long-chain alkyl compound has a carbon atom number of 6-20.

3. The integrated electrochromic device of claim 1 or 2, wherein, The long-chain alkyl compound is selected from one or more of alkyl imidazole salt, alkyl pyridine salt, alkyl pyrrole salt, alkyl quaternary ammonium salt, alkyl quaternary phosphonium salt, fluoroalkyl imidazole salt, fluoroalkyl pyridine salt, fluoroalkyl pyrrole salt, fluoroalkyl quaternary ammonium salt, and fluoroalkyl quaternary phosphonium salt.

4. The integrated electrochromic device of claim 3, wherein the at least one of the first and second electrodes is a transparent electrode. The long-chain alkyl compound is selected from one or more of 1-C6-C20 alkyl-3-methyl imidazole salt, 1-vinyl-3-C6-C20 alkyl imidazole salt, and N-C6-C20 alkyl pyridine salt. The anion of the long-chain alkyl compound is selected from halogen ion, tetrafluoroborate ion, hexafluorophosphate ion, fluorosulfonimide ion, trifluoromethanesulfonimide ion, and bistrifluoromethanesulfonimide ion.

5. The integrated electrochromic device of claim 1, wherein, The ionic liquid has a mass content of 20-90% in the integrated electrochromic reflective layer.

6. The integrated electrochromic device of claim 1, wherein, The integrated electrochromic reflective layer further comprises a metal source, and one or more of a polymer compound, a solvent, and an additive.

7. The integrated electrochromic device of claim 6, wherein, The metal source is selected from one or more of silver chloride, silver bromide, silver iodide, silver acetate, silver nitrate, silver perchlorate, silver perbromate, silver periodate, silver sulfate, silver cyanide, silver sulfide, silver hexafluorophosphate, silver tetrafluoroborate, silver tetrachloroaluminate, silver trifluoromethanesulfonate, silver bistrifluoromethanesulfonimide, copper fluoride, copper chloride, copper bromide, copper iodide, copper cyanide, copper sulfate, copper acetate, copper aluminate, cuprous fluoride, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, gold chloride, gold cyanide, gold sulfide, aurous chloride, aurous sulfide, nickel chloride, nickel sulfate, cobalt chloride, platinum chloride. The polymer compound comprises one or more of polyacrylic acid and its derivatives, polyacrylate and its derivatives, polyhydroxyethyl acrylate and its derivatives, polyvinyl pyrrolidone and its derivatives, polyurethane and its derivatives, polyepoxy resin and its derivatives, and copolymers of the above polymers. The solvent is selected from one or more of γ-butyrolactone and its derivatives, dimethyl sulfoxide and its derivatives, N-methyl pyrrolidone and its derivatives, N,N-dimethylacetamide and its derivatives, N,N-dimethylformamide and its derivatives, cyclopentyl methyl ether and its derivatives, cyclobutyl sulfone and its derivatives, propylene carbonate and its derivatives, ethylene carbonate and its derivatives, and ethylene glycol dimethyl ether and its derivatives. The additive comprises one or more of a coupling agent, an antioxidant, a light stabilizer, a thickening agent, a supplemental electrolyte, and a spacer.

8. The integrated electrochromic device of claim 1, wherein, The integrated electrochromic reflective device comprises, in sequence: a first substrate layer, a working electrode layer, an integrated electrochromic reflective layer, a counter electrode layer, and a second substrate layer. The first substrate layer and the second substrate layer are independently selected from inorganic substrate, organic substrate, or inorganic-organic composite substrate. The conductive layer material of the working electrode layer is selected from one or more of indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, nano-copper wire, nano-silver wire, nano-aluminum wire, metal copper grid, metal silver grid, metal aluminum grid, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, graphene, carbon nanotube, and nano-silver paste; The conductive layer material of the counter electrode layer is selected from one or more of nano-copper wire, nano-silver wire, nano-aluminum wire, metal copper grid, metal silver grid, metal aluminum grid, indium tin oxide-copper multilayer composite material, indium tin oxide-silver multilayer composite material, indium tin oxide-aluminum multilayer composite material, and nano-silver paste.

9. A method for preparing the integrated electrochromic device according to any one of claims 1 to 8, comprising the following steps: S1) coating the integrated electrochromic layer solution or slurry on the surface of the counter electrode or working electrode, forming a film and solidifying the solution or slurry; S2) laser slicing, electrode pasting, and packaging to obtain the integrated electrochromic device; or comprising the following steps: S11) punching a pre-made hole on the rigid conductive substrate, pasting the working electrode plate and the counter electrode plate face to face, using a spacer to control the distance between the plates to form a hollow device shell; S22) injecting the integrated electrochromic layer solution or slurry into the hollow device shell through the pre-made hole; S33) dispensing and sealing, and solidifying the solution or slurry to obtain the integrated electrochromic device.

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