Ion transport layer, electrochromic device and application of electrochromic device

Abstract

The invention discloses an ion transport layer, an electrochromic device and application of the electrochromic device.The ion transport layer comprises composite nano-particles, the composite nano-particles comprise heat insulation nano-particles and an insulating layer, the insulating layer wraps the surfaces of the heat insulation nano-particles, the thickness of the insulating layer is d, the radius of the heat insulation nano-particles is R1, and the radius of the heat insulation nano-particles is R2. The radiuses of the composite nanoparticles are R2 and d, and R1 and R2 meet the following conditions: d = R2-R1, and d is more than 0 and less than or equal to R1. According to the ion transport layer, the ion moving speed of the ion transport layer is guaranteed, the electrochromic response efficiency is improved, the power-on cycle life is prolonged, meanwhile, the thickness of the insulating layer is limited, the heat insulation performance of the corresponding ion transport layer is improved, and the service life of the ion transport layer is prolonged. The short-circuit risk of the electrochromic device caused by aggregation among the heat-insulating nano-particles can be avoided through the insulating layer of the heat-insulating nano-particles, and meanwhile, the change of the optical performance of the ion transmission layer and the corresponding electrochromic device is reduced.

Description

Technical Field

[0001] This invention relates to the field of electrochromic technology, and in particular to an ion transport layer, an electrochromic device, and the application of the electrochromic device. Background Technology

[0002] The structure of an electrochromic device typically consists of, in sequence, a glass or transparent substrate, a transparent conductive layer, an electrochromic layer, an ion transport layer, an ion storage layer, another transparent conductive layer, and a glass or transparent substrate. Electrochromic devices themselves have relatively poor thermal insulation properties. External physical protection methods, such as high-temperature, high-pressure lamination processes or vacuum magnetosputtering coating technology, are often used to improve their thermal insulation performance. However, the lack of thermal insulation properties in the ion transport layer itself is the main factor limiting the device's thermal insulation performance.

[0003] In related technologies, functional conductive nanoparticles with reflective and heat-insulating properties are often added to the ion transport layer to improve the heat insulation performance of the ion transport layer in electrochromic devices. However, these functional conductive nanoparticles have extremely high surface energy, and their direct addition to conductive polymers can easily lead to aggregation and short circuits in the electrochromic devices. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, one object of the present invention is to provide an ion transport layer that improves the thermal insulation performance of the corresponding ion transport layer, and at the same time avoids the risk of short circuit in electrochromic devices caused by the aggregation of thermal insulation nanoparticles due to the insulating layer of thermal insulation nanoparticles.

[0005] Another object of the present invention is to provide an electrochromic device.

[0006] Another object of the present invention is to provide an application of an electrochromic device.

[0007] According to a first aspect of the present invention, an ion transport layer includes: composite nanoparticles, the composite nanoparticles including heat-insulating nanoparticles and an insulating layer, the insulating layer covering the surface of the heat-insulating nanoparticles, wherein the thickness of the insulating layer is d, the radius of the heat-insulating nanoparticles is R1, the radius of the composite nanoparticles is R2, and d, R1 and R2 satisfy: d = R2 - R1, 0 < d ≤ R1.

[0008] According to an embodiment of the present invention, the ion transport layer is formed by using an insulating layer to coat thermally insulating nanoparticles to ensure the ion movement speed of the ion transport layer, improve the electrochromic response efficiency, and extend the cycle life. At the same time, the thickness of the insulating layer is limited, which not only improves the thermal insulation performance of the corresponding ion transport layer, but also avoids the risk of short circuit in the electrochromic device caused by the aggregation of thermally insulating nanoparticles through the insulating layer of the thermally insulating nanoparticles. It also reduces the changes in the optical performance of the ion transport layer and the corresponding electrochromic device.

[0009] According to some embodiments of the present invention, the thermally insulating nanoparticles account for 2% to 5% of the ion transport layer by mass percentage.

[0010] According to some embodiments of the present invention, the radius R1 of the heat-insulating nanoparticles satisfies: 20nm≤R1≤120nm.

[0011] According to some embodiments of the present invention, the weight of the insulating layer accounts for 10% to 50% of the weight of the composite nanoparticles.

[0012] According to some embodiments of the present invention, the weight of the insulating layer accounts for 10% to 30% of the weight of the composite nanoparticles.

[0013] According to some embodiments of the present invention, the heat-insulating nanoparticles include at least one of nano-Cu, nano-Ag, nano-ATO, nano-ITO and nano-AZO.

[0014] According to some embodiments of the present invention, the insulating layer comprises at least one of a surfactant, a coupling agent, or a nanodispersion.

[0015] According to some embodiments of the present invention, the surfactant includes at least one of polyether surfactants, polyol surfactants, polyester surfactants, and polyethylene nonionic surfactants.

[0016] According to some embodiments of the present invention, the polyether surfactant includes polyvinylpyrrolidone, polyethylene glycol, propylene glycol block polyether, propanol polyoxyalkylene ether, isotretinoin random polyether, glycerol random polyether, lauryl alcohol random polyether; and / or, the polyester surfactant includes at least one of polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, and polybutylene succinate.

[0017] According to some embodiments of the present invention, the coupling agent includes at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, and phosphate coupling agents; and / or, the nano-dispersion includes at least one of nano-chitosan dispersion, nano-cellulose dispersion, nano-aluminum sol dispersion, nano-silica sol, graphene oxide dispersion, and carbon nanotube dispersion.

[0018] According to some embodiments of the present invention, the silane coupling agent comprises: methyltrimethoxysilane, methyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, γ-glycidyl etheroxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, etc. At least one of the following: oxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, N-(β-aminoethyl-γ-aminopropyl)trimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; and / or, the titanate coupling agent comprises: isobutyl triisostearoyl titanate, isopropyltrimethoxysilane, etc. At least one of the following: (dioctylpyrophosphate)titanate, isopropyltris(dodecylbenzenesulfonyl)titanate, isopropyltriisostearate isobutyl titanate, bis(triethanolamine)diisopropoxytitanate, bis(acetylacetonyl)diisopropoxytitanate, bis(acetylacetonyl)ethoxyisopropoxytitanate, bis(acetylacetonyl)isobutoxyisopropoxytitanate, bis(ethyl acetoacetate)diisopropoxytitanate, and bis(ethyl acetoacetate)diisobutoxytitanate; and / or, the aluminate coupling agent comprises at least one of: isopropyl distearate aluminate, aluminate coupling agent DL-411, aluminate coupling agent DL-411AF, aluminate coupling agent DL-411D, and aluminate coupling agent DL-411DF; and / or, the phosphate coupling agent comprises: alkyl dihydrogen phosphate, ethylidene methacrylate phosphate, phenylalkyl diester phosphate, and phenyl phosphate.

[0019] According to some embodiments of the present invention, the ion transport layer further includes a conductive medium, a UV curing agent, and a resin.

[0020] According to some embodiments of the present invention, the conductive medium comprises small organic molecules and soluble conductive salts.

[0021] According to some embodiments of the present invention, the soluble conductive salt is an organic lithium salt, which includes at least one of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium toluenesulfonate, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, and lithium bis(fluorosulfonyl)imide; and / or, the organic small molecule includes at least one of propylene carbonate, ethylene carbonate, acetonitrile, ethylene ethylene carbonate, ethylene carbonate, N,N-dimethylformamide, dimethyl carbonate, methyl ethyl carbonate, butanediol, propylene glycol, and dimethyl propylene glycol.

[0022] According to some embodiments of the present invention, the UV curing agent includes at least one selected from 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0023] According to some embodiments of the present invention, the resin comprises at least one of acrylate-based and polyurethane-based resins.

[0024] An electrochromic device according to a second aspect of the present invention includes: a transparent conductive layer, an electrochromic layer, an ion transport layer, an ion storage layer, and a transparent conductive layer sequentially along the thickness direction, wherein the ion transport layer is the ion transport layer according to the first aspect of the present invention described above.

[0025] According to some embodiments of the present invention, the ion storage layer comprises at least one of vanadium pentoxide, nickel oxide, tungsten oxide, niobium pentoxide, and cerium oxide; and / or, the electrochromic layer comprises at least one of poly(2,5-dibromo-3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-bis(4-ethylhexyloxy)thiophene), polypyrrole, polyaniline, polystyrene sulfonate, di-(2-phosphonoethyl)-4,4'-bispyridine, 1,1'-dimethyl-4,4'-bispyridine, molybdenum oxide, tungsten oxide, and titanium oxide.

[0026] According to a third aspect of the present invention, the electrochromic device is used in electronic and electrical components, automobile windows, rearview mirrors, and architectural glass windows.

[0027] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0028] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0029] Figure 1 This is a schematic diagram of composite nanoparticles according to an embodiment of the present invention.

[0030] Figure label:

[0031] 100: Composite nanoparticles;

[0032] 1: Heat-insulating nanoparticles; 2: Insulating layer. Detailed Implementation

[0033] The following is for reference. Figure 1 An ion transport layer according to an embodiment of the first aspect of the present invention is described.

[0034] like Figure 1 As shown, the ion transport layer according to the first aspect of the present invention includes composite nanoparticles 100. The composite nanoparticles 100 include heat-insulating nanoparticles 1 and an insulating layer 2. The insulating layer 2 covers the surface of the heat-insulating nanoparticles 1. The thickness of the insulating layer 2 is d, the radius of the heat-insulating nanoparticles 1 is R1, and the radius of the composite nanoparticles 100 is R2. d, R1, and R2 satisfy: d = R2 - R1, 0 < d ≤ R1.

[0035] Specifically, the insulating layer 2 is coated on the outer surface of the heat-insulating nanoparticles 1, which helps to prevent the heat-insulating nanoparticles 1 from being directly exposed, thereby preventing the heat-insulating nanoparticles 1 from agglomerating, preventing short circuits in the ion transport layer or even the electrochromic device, ensuring the optical performance of the ion transport layer, and at the same time helping to improve the heat insulation performance of the ion transport layer and the electrochromic device.

[0036] When d = 0, the heat-insulating nanoparticles 1 are difficult to exist stably in the polymer network; when d > R1, the heat insulation performance of the corresponding ion transport layer begins to decline, and the composite nanoparticles 100 exhibit the properties of the insulating layer 2. The greater the thickness of the insulating layer 2, the worse the heat insulation effect, and the optical performance of the corresponding electrochromic device will also be affected, such as increased haze and reduced transmittance. Therefore, by controlling the thickness of the insulating layer 2 to 0 < d ≤ R1, the proportion of heat-insulating nanoparticles 1 in the ion transport layer is increased, thereby improving the heat insulation performance of the corresponding ion transport layer. At the same time, the insulating layer 2 of the heat-insulating nanoparticles 1 can prevent the aggregation of heat-insulating nanoparticles 1, which could cause short circuits in the electrochromic device. Furthermore, under this condition, the optical performance of the corresponding ion transport layer and the electrochromic device is almost unaffected.

[0037] According to an embodiment of the present invention, the ion transport layer uses an insulating layer 2 to coat the composite nanoparticles 100 formed by the thermally insulating nanoparticles 1, thereby ensuring the ion movement speed of the ion transport layer, improving the electrochromic response efficiency, and extending the cycle life. At the same time, the thickness of the insulating layer 2 is limited, which not only improves the thermal insulation performance of the corresponding ion transport layer, but also avoids the risk of short circuit in the electrochromic device caused by the aggregation of the thermally insulating nanoparticles 1 through the insulating layer 2 of the thermally insulating nanoparticles 1. At the same time, it reduces the changes in the optical performance of the ion transport layer and the corresponding electrochromic device.

[0038] According to some embodiments of the present invention, with reference to Figure 1 The thermal insulation nanoparticles 1 account for 2% to 5% of the ion transport layer by mass percentage. Therefore, the amount of thermal insulation nanoparticles 1 added to the ion transport layer is reasonable, which can fully meet the thermal insulation requirements of the ion transport layer while also meeting the requirements for improving the optical performance of the ion transport layer.

[0039] The radius R1 of the thermal insulation nanoparticle 1 satisfies: 20nm ≤ R1 ≤ 120nm. The radius of the thermal insulation nanoparticle 1 is relatively reasonable, which reduces the difficulty of production while meeting the conductivity requirements, thus helping to control the preparation cost of the ion transport layer.

[0040] The weight of the insulating layer 2 accounts for 10% to 50% of the weight of the composite nanoparticles 100. The content of the insulating layer 2 in the composite nanoparticles 100 is set reasonably, which helps to ensure that the thickness of the insulating layer 2 is reasonable, helps to give full play to the protective role of the insulating layer 2 for the heat-insulating nanoparticles 1, helps to reduce the short-circuit risk of electrochromic devices caused by the aggregation of heat-insulating nanoparticles 1, and at the same time helps to give full play to the role of the insulating layer 2.

[0041] Preferably, the weight of the insulating layer 2 accounts for 10% to 30% of the weight of the composite nanoparticles 100.

[0042] Furthermore, the heat-insulating nanoparticles 1 include at least one of nano-Cu, nano-Ag, nano-ATO, nano-ITO, and nano-AZO. The aforementioned heat-insulating nanoparticles 1 all exhibit good electrical conductivity, a large specific surface area and volume ratio, and high reactivity. Simultaneously, the cost of the aforementioned heat-insulating nanoparticles 1 is low. Therefore, using at least one of the aforementioned heat-insulating nanoparticles 1 is beneficial for ensuring the optical performance of the electron transport layer while controlling the cost of the ion transport layer.

[0043] According to some embodiments of the present invention, the insulating layer 2 comprises at least one of a surfactant, a coupling agent, or a nano-dispersion. The surfactant helps to better disperse the composite nanoparticles 100, reducing voids and defects, thereby improving the insulation performance of the insulating layer 2. Simultaneously, the surfactant improves the processability of the insulating layer 2. Furthermore, the surfactant increases the compatibility between the composite nanoparticles 100 and other components in the insulating layer 2, thereby enhancing the overall integrity of the insulating layer 2. The coupling agent improves the performance of the insulating layer 2, particularly enhancing the bonding force between multiple components in the insulating layer 2, thereby improving the mechanical strength, heat resistance, and electrical insulation performance of the insulating layer 2. The nano-dispersion improves the dielectric constant, breakdown voltage, and electrical insulation strength of the insulating layer 2, while also improving its mechanical strength, toughness, and wear resistance. Therefore, using at least one of a surfactant, coupling agent, or nano-dispersion is beneficial for improving the mechanical strength and insulation performance of the insulating layer 2, thereby improving the quality of the insulating layer 2.

[0044] Furthermore, the surfactant includes at least one of the following: polyether surfactants, polyol surfactants, polyester surfactants, and polyethylene nonionic surfactants. All of these surfactants possess good surface activity and good dispersing properties, and also exhibit good chemical stability. Using at least one of these surfactants is beneficial for improving the uniformity and processing consistency of the insulating layer 2, thereby enhancing the quality of the ion transport layer.

[0045] Furthermore, the polyether surfactants include polyvinylpyrrolidone, polyethylene glycol, propylene glycol block polyether, propanol polyoxyalkylene ether, isotridecyl alcohol random polyether, glycerol random polyether, lauryl alcohol random polyether; and / or, the polyester surfactants include at least one of polyethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, and polybutylene succinate. The aforementioned polyether surfactants and / or polyester surfactants exhibit high surface activity, good chemical stability, good water solubility, and are easily dispersed. Using at least one of these organic compounds as a surfactant is beneficial for improving the quality of the insulation layer 2 while simultaneously reducing the preparation cost of the insulation layer 2.

[0046] According to some embodiments of the present invention, the coupling agent includes at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, and phosphate coupling agents. All of the above coupling agents can form a layer of coupling agent molecules on the surface of the composite nanoparticles 100, which is beneficial for enhancing the compatibility of various components in the insulating layer 2, and can also improve the electrical insulation, mechanical strength, and chemical resistance of the insulating layer 2.

[0047] The nano-dispersions include at least one of the following: nano-chitosan dispersions, nano-cellulose dispersions, nano-aluminum sol dispersions, nano-silica sols, graphene oxide dispersions, and carbon oxide nanotube dispersions. All of the above nano-dispersions exhibit good dispersibility, which is beneficial for improving the uniformity of the insulating layer 2. Furthermore, these nano-dispersions contribute to improving the mechanical strength and toughness of the insulating layer 2.

[0048] Further, the silane coupling agent includes at least one of the following: methyltrimethoxysilane, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, N-(β-aminoethyl-γ-aminopropyl)trimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. The two ends of the silane coupling agent have different functional groups. For example, one end is a silane group and the other end is an organic functional group (such as amino, epoxy, methacryloxy, etc.). This is beneficial to enhance the interfacial adhesion between the various components of the insulating layer 2, reduce the occurrence of agglomeration, thereby improving the quality of the insulating layer 2, and further improving the thermal insulation stability and reliability of the ion transport layer.

[0049] Titanate coupling agents include at least one of the following: triisostearoyl titanate isobutyl, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, isopropyl triisostearoyl titanate isobutyl, bis(triethanolamine)diisopropoxy titanate, bis(acetylacetonyl)diisopropoxy titanate, bis(acetylacetonyl)ethoxyisopropoxy titanate, bis(acetylacetonyl)isobutoxyisopropoxy titanate, bis(ethyl acetoacetate)diisopropoxy titanate, and bis(ethyl acetoacetate)diisobutoxy titanate. The titanate coupling agent has different functional groups at both ends; one end is a titanate group, and the other end is an organic functional group. Using at least one of the above titanate coupling agents is beneficial for enhancing the chemical stability, heat resistance, and mechanical strength of the insulating layer 2.

[0050] The aluminate coupling agent includes at least one of the following: isopropyl distearate, aluminate coupling agent DL-411, aluminate coupling agent DL-411AF, aluminate coupling agent DL-411D, and aluminate coupling agent DL-411DF. The two ends of the above aluminate coupling agents are different functional groups; one end is an aluminate group, and the other end is an organic functional group. The above aluminate coupling agents exhibit good chemical stability, which is beneficial for improving the mechanical properties of the insulating layer 2, thereby enhancing the thermal insulation performance of the composite nanoparticles 100.

[0051] Phosphate ester coupling agents include: alkyl dihydrogen phosphate, ethylidene methacrylate phosphate, phenyl alkyl diester phosphate, and phenyl phosphate. The two ends of the phosphate ester coupling agent are different functional groups; one end is a phosphate ester group, and the other end is an organic functional group. Using at least one of the above-mentioned phosphate ester coupling agents is beneficial for improving the mechanical strength, heat resistance, and electrical insulation properties of the insulating layer 2.

[0052] According to some embodiments of the present invention, the ion transport layer further includes a conductive medium, a UV curing agent, and a remaining resin. The conductive medium provides an ion conduction path, promoting rapid ion migration within the ion transport layer, thereby improving the current density and power output of the ion transport layer. The UV curing agent generates free radicals under ultraviolet light stimulation, causing the active functional groups in the resin to polymerize and form a cross-linked cured molecular network with better chemical and thermal stability, thus improving the bonding force of the ion transport layer. The resin can serve as a matrix material, providing structural support for the ion transport layer, and also as a carrier, supporting components such as the conductive medium and the UV curing agent.

[0053] The ion transport layer comprises, by mass percentage, 20%–30% conductive dielectric, 0.5%–1% UV curing agent, and the balance resin.

[0054] Furthermore, the conductive medium includes small organic molecules and soluble conductive salts. These small organic molecules and soluble conductive salts can improve the ionic conductivity of the ion transport layer, thereby increasing energy conversion efficiency. Simultaneously, they can enhance the chemical and thermal stability of the ion transport layer. Specifically, the ion transport layer comprises 4%–6% soluble conductive salts by mass percentage.

[0055] Furthermore, the soluble conductive salt is an organic lithium salt, including at least one of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium toluenesulfonate, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, and lithium bis(trifluoromethanesulfonyl)imide. The above-mentioned soluble conductive salts have good solubility, which is beneficial for improving the ionic conductivity of the ion transport layer. At the same time, the cost of these soluble conductive salts is relatively low, thus helping to control the preparation cost of the ion transport layer.

[0056] The organic small molecules include at least one selected from propylene carbonate, ethylene carbonate, acetonitrile, ethylene ethylene carbonate, ethylene carbonate, N,N-dimethylformamide, dimethyl carbonate, methyl ethyl carbonate, butanediol, propylene glycol, and dimethyl propylene glycol. These organic small molecules have good dielectric constants. Using these organic small molecules is beneficial for improving the conductivity of the conductive medium, thereby improving the conductivity of the ion-conducting layer and thus enhancing the performance of electrochromic devices using the aforementioned ion transport layer.

[0057] According to some embodiments of the present invention, the UV curing agent includes at least one selected from 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate. All of the above UV curing agents are suitable for curing under ultraviolet light and exhibit good compatibility with other components in the ion transport layer. Therefore, using at least one of the above UV curing agents is beneficial for improving the depth and reliability of the ion transport layer, thereby enhancing the structural stability and reliability of the ion transport layer.

[0058] Furthermore, the resin includes at least one of acrylate-based and polyurethane-based resins. These resins are beneficial for improving the ionic conductivity of the ion transport layer, thereby increasing energy conversion efficiency. Simultaneously, the resins can enhance the flexibility, heat resistance, and transparency of the ion transport layer.

[0059] An electrochromic device according to a second aspect of the present invention includes: a transparent conductive layer, an electrochromic layer, an ion transport layer, an ion storage layer, and a transparent conductive layer sequentially along the thickness direction, wherein the ion transport layer is the ion transport layer according to the first aspect of the present invention described above.

[0060] According to an embodiment of the electrochromic device of the present invention, light can pass through a transparent conductive layer onto the electrochromic layer and the ion transport layer. The ion storage layer is used to store and provide ions required during the electrochromic process. When an external electric field is applied to the ion storage layer, the ion storage layer and the electrochromic layer work together to achieve reversible color changes.

[0061] Furthermore, the ion storage layer includes at least one of vanadium pentoxide, nickel oxide, tungsten oxide, niobium pentoxide, and cerium oxide. All of these components possess good ionic conductivity and chemical stability, and are also suitable for capturing and releasing ions. Therefore, when an external electric field is applied to the electrochromic layer, the ion storage layer releases ions into the electrochromic layer, causing a color change in the electrochromic layer; when the electric field direction is reversed, the ions return from the electrochromic layer to the ion storage layer, causing the electrochromic device to return to its original color state. This enables long-term cyclic use of the electrochromic device.

[0062] The electrochromic layer comprises at least one of the following: poly(2,5-dibromo-3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-bis(4-ethylhexyloxy)thiophene), polypyrrole, polyaniline, polystyrene sulfonate, bis-(2-phosphonoethyl)-4,4'-bispyridine, 1,1'-dimethyl-4,4'-bispyridine, molybdenum oxide, tungsten oxide, and titanium oxide. These materials exhibit good thermal and chemical stability, high tunability, and ease of processing. Therefore, employing at least one of these materials helps ensure the stability of the electrochromic layer during use, thereby facilitating the stable and reliable operation of electrochromic devices.

[0063] According to the third aspect of the present invention, the electrochromic device is used in electronic and electrical components, automobile windows, rearview mirrors and building windows.

[0064] The electrochromic devices according to embodiments of the present invention have a wide range of applications, which helps to improve the applicability of electrochromic devices and enhance their market competitiveness.

[0065] The embodiments of the present invention are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. In addition, unless otherwise specified, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known to others. For reaction conditions not listed, they are also readily available to those skilled in the art.

[0066] The specific data of R1 (nm), radius R2 (nm) of composite nanoparticles, and thickness d (nm) of insulating layer for the thermal insulating nanoparticles of Examples 1-8 and Comparative Examples 1-8 are shown in Table 1.

[0067] Example 1

[0068] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0069] Take 0.2g of 3-mercaptopropyltrimethoxysilane and add it to 8g of isopropanol and 2g of ultrapure water. Then add 1g of Cu nanoparticles with a radius of 30nm. Stir the reaction at 40℃ for 1h, then sonicate for 30min. Finally, centrifuge, wash and dry to obtain silane-coated copper nanoparticles.

[0070] ②Preparation of adhesive for ion transport layers

[0071] Take 2g of the core-shell structured nanoparticles prepared according to method ① and add them to 70g of polyurethane-based resin. Then, add 27.5g of propylene carbonate solution containing 6g of 1-butyl-3-methylimidazolium hexafluorophosphate and 0.5g of UV curing agent, disperse and mix evenly, and set aside for later use.

[0072] ③ Assemble electrochromic devices

[0073] The ion transport layer prepared in step ② is applied between the electrochromic layer and the ion storage layer using liquid adhesive and cured under UV light to obtain an electrochromic device with heat insulation function, which has a layered structure from top to bottom as glass or transparent substrate, transparent conductive layer, electrochromic layer, ion transport layer, ion storage layer and transparent conductive layer and glass or transparent substrate.

[0074] Example 2

[0075] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0076] 0.6g of 3-mercaptopropyltrimethoxysilane was added to 8g of isopropanol and 2g of ultrapure water, and then 1g of 30nm-radius Cu nanoparticles were added. The mixture was stirred at 40℃ for 1h, then ultrasonically dispersed for 30min, and finally centrifuged, washed and dried to obtain silane-coated copper nanoparticles.

[0077] Steps ② and ③ are consistent with those in Example 1.

[0078] Example 3

[0079] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0080] Add 0.3g of polyvinylpyrrolidone to 20g of ethylene glycol and 5g of ultrapure water, then add 10g of 30nm-radius Cu nanoparticles, stir and react at 60℃ for 3h, then ultrasonically disperse, and finally centrifuge, wash and dry to obtain surfactant-coated nano-copper.

[0081] ②Preparation of adhesive for ion transport layers

[0082] Take 3g of the core-shell structured nanoparticles prepared according to method ① and add them to 70g of acrylic resin. Then, add 26.5g of ethylene carbonate solution containing 6g of lithium bis(trifluoromethanesulfonylimide) and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0083] ③ Assemble electrochromic devices

[0084] The specific steps are the same as in Example 1.

[0085] Example 4

[0086] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0087] Take 0.9g of polyvinylpyrrolidone and add it to 20g of ethylene glycol and 5g of ultrapure water. Then add 1g of 30nm nano-Cu particles. Stir and react at 60℃ for 3h. Then disperse by ultrasonication. Finally, centrifuge, wash and dry to obtain surfactant-coated nano-copper.

[0088] ②Preparation of adhesive for ion transport layers

[0089] The specific steps are the same as in Example 3.

[0090] ③ Assemble electrochromic devices

[0091] The specific steps are the same as in Example 1.

[0092] Example 5

[0093] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0094] 0.1g of isopropyltris(dioctylpyrophosphoryloxy)titanate was added to 15g of ethanol, and then 1g of nano-ITO particles with a radius of 50nm were added. The mixture was stirred at 50℃ for 3h, then ultrasonically dispersed, and finally centrifuged, washed and dried to obtain the nano-ITO particles coated with titanate.

[0095] ②Preparation of adhesive for ion transport layers

[0096] Take 5g of the core-shell structured nanoparticles prepared according to method ① and add them to 70g of acrylic resin. Then, add 24.5g of ethylene carbonate solution containing 6g of lithium bis(trifluoromethanesulfonylimide) and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0097] ③ Assemble electrochromic devices

[0098] The specific steps are the same as in Example 1.

[0099] Example 6

[0100] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0101] Take 0.3g of isopropyltris(dioctylpyrophosphoryloxy)titanate and add it to 15g of ethanol. Then add 1g of nano-ITO particles with a radius of 50nm. Stir and react at 50℃ for 3h. Then disperse by ultrasonication. Finally, centrifuge, wash and dry to obtain nano-ITO particles coated with titanate.

[0102] ②Preparation of adhesive for ion transport layers

[0103] The specific steps are the same as in Example 5.

[0104] ③ Assemble electrochromic devices

[0105] The specific steps are the same as in Example 1.

[0106] Example 7

[0107] ① Dissolve 0.3g of nano-chitosan in 50g of 1% acetic acid solution, then add 1g of nano-Ag particles with a radius of 20nm, stir and react at 140℃ for 3h, then disperse by ultrasonication, and finally centrifuge, wash and dry to obtain nano-Ag particles coated with nano-chitosan.

[0108] ②Preparation of adhesive for ion transport layers

[0109] Take 3g of the core-shell structured nanoparticles prepared according to method ① and add them to 70g of polyurethane acrylic resin. Then, add 26.5g of vinylene carbonate solution containing 6g of 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0110] ③ Assemble electrochromic devices

[0111] The specific steps are the same as in Example 1.

[0112] Example 8

[0113] Dissolve 0.9g of nano-chitosan in 50g of 1% acetic acid solution, then add 1g of nano-Ag particles with a radius of 20nm, stir and react at 140℃ for 3h, then ultrasonically disperse, and finally centrifuge, wash and dry to obtain nano-Ag particles coated with nano-chitosan.

[0114] ②Preparation of adhesive for ion transport layers

[0115] The specific steps are the same as in Example 7.

[0116] ③ Assemble electrochromic devices

[0117] The specific steps are the same as in Example 1.

[0118] Comparative Example 1

[0119] ①Preparation of adhesives for ion transport layers

[0120] Take 2g of uncoated 30nm nano-Cu particles and add them to 70g of polyurethane-based resin. Then, add 27.5g of propylene carbonate solution containing 6g of 1-butyl-3-methylimidazolium hexafluorophosphate and 0.5g of UV curing agent, disperse and mix evenly, and set aside for later use.

[0121] ② Assemble electrochromic devices

[0122] The specific steps are the same as in Example 1.

[0123] Comparative Example 2

[0124] ① Preparation of composite nanoparticles 100 with insulating layer 2 coating thermal insulating nanoparticles 1

[0125] Take 0.8g of 3-mercaptopropyltrimethoxysilane and add it to 8g of isopropanol and 2g of ultrapure water. Then add 10g of 30nm nano-Cu particles, stir and grind for 30min, and then centrifuge, wash and dry to obtain silane-coated nano-copper.

[0126] Steps ② and ③ are consistent with those in Example 1.

[0127] Comparative Example 3

[0128] ①Preparation of adhesives for ion transport layers

[0129] Take 3g of uncoated nanoparticles and add them to 70g of acrylic resin. Then, add 26.5g of ethylene carbonate solution containing 6g of lithium bis(trifluoromethanesulfonylimide) and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0130] ③ Assemble electrochromic devices

[0131] The specific steps are the same as in Example 3.

[0132] Comparative Example 4

[0133] ① Preparation of insulating layer 2 to coat heat-insulating nanoparticles 1 corresponding to core-shell structure nanoparticles

[0134] Add 2g of polyvinylpyrrolidone to 20g of ethylene glycol and 5g of ultrapure water, then add 10g of 30nm-radius Cu nanoparticles, stir and react at 60℃ for 3h, then ultrasonically disperse, and finally centrifuge, wash and dry to obtain surfactant-coated nano-copper.

[0135] ②Preparation of adhesive for ion transport layers

[0136] For specific steps, please refer to Example 3.

[0137] ③ Assemble electrochromic devices

[0138] The specific steps are the same as in Example 3.

[0139] Comparative Example 5

[0140] ①Preparation of adhesives for ion transport layers

[0141] Take 5g of uncoated ITO nanoparticles and add them to 70g of acrylic resin. Then add 24.5g of ethylene carbonate solution containing 6g of lithium bis(trifluoromethanesulfonyl)imide and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0142] ② Assemble electrochromic devices

[0143] The specific steps are the same as in Example 5.

[0144] Comparative Example 6

[0145] ① Preparation of insulating layer 2 to coat heat-insulating nanoparticles 1 corresponding to core-shell structure nanoparticles

[0146] Take 0.5g of isopropyltris(dioctylpyrophosphoryloxy)titanate and add it to 15g of ethanol. Then add 1g of nano-ITO particles with a radius of 50nm. Stir and react at 50℃ for 3h. Then disperse by ultrasonication. Finally, centrifuge, wash and dry to obtain nano-ITO particles coated with titanate.

[0147] ②Preparation of adhesive for ion transport layers

[0148] For specific steps, please refer to Example 5.

[0149] ③ Assemble electrochromic devices

[0150] The specific steps are the same as in Example 5.

[0151] Comparative Example 7

[0152] ①Preparation of adhesives for ion transport layers

[0153] Take 3g of uncoated Ag nanoparticles and add them to 70g of polyurethane acrylic resin. Then, add 26.5g of vinylene carbonate solution containing 6g of 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate and 0.5g of UV curing agent and disperse evenly. Set aside for later use.

[0154] ② Assemble electrochromic devices

[0155] The specific steps are the same as in Example 7.

[0156] Comparative Example 8

[0157] ① Dissolve 1.2g of nano-chitosan in 50g of 1% acetic acid solution, then add 1g of nano-Ag particles with a radius of 20nm, stir and react at 140℃ for 3h, then ultrasonically disperse, and finally centrifuge, wash and dry to obtain nano-Ag particles coated with nano-chitosan.

[0158] ②Preparation of adhesive for ion transport layers

[0159] For specific steps, please refer to Example 7.

[0160] ③ Assemble electrochromic devices

[0161] The specific steps are the same as in Example 7.

[0162] Table 1 shows the data for Embodiments 1-8 and Comparative Examples 1-8 of this disclosure.

[0163]

[0164]

[0165] Performance testing

[0166] ① Select the above-mentioned electrochromic device with a size of 10cm*10cm, then connect an adjustable positive and negative voltage of 1.1V, and measure the response time t1 of the electrochromic device from the fading state to the colored state (+1.1V) and the response time t2 from the colored state to the fading state (-1.1V) under the transmission and reflection spectrometer. Take the average value of t1 and t2 as the response time t of the electrochromic device.

[0167] Among them, at a voltage of 1.1V, the average response time of the electrochromic device in different directions is t≤4s, which means the color change response speed is excellent; the average response time is 4s<t≤7s, which means the color change response speed is good; the average response time is 7s<t≤10s, which means the color change response speed is qualified; and the average response time is t>10s or no color change, which means the color change response speed is unqualified.

[0168] ② Using an electrochemical workstation, set the response time for the corresponding examples and comparative examples. From the fading state to the coloring state, and then from the coloring state to the fading state, record this as one cycle. Repeat the cycle 10,000 times, observe the color uniformity of the corresponding electrochromic device, and record the color difference ΔE of the electrochromic device before and after the cycle. When ΔE≤3, the electrochromic device can still change color uniformly and gradually, which is considered qualified. If ΔE>3 and / or if texture, local preferential color change, no color change, or short circuit occurs during the color change process, it is considered unqualified.

[0169] Test method for heat insulation effect: Refer to GB / T 2680-1994 or ISO9050:2003, place the electrochromic devices composed of the corresponding embodiments and comparative examples in an optical testing device for testing and calculate the heat insulation efficiency of the corresponding components.

[0170] Test Result Analysis

[0171] Referring to Examples 1-8 and Comparative Examples 1-8, when the composite nanoparticles in the ion transport layer satisfy the condition 0 < d ≤ R1, the corresponding electrochromic device can simultaneously meet the requirements for both color-changing and heat-insulating effects. Referring to Comparative Example 1, when the conductive Cu nanoparticles are not coated, at d = 0, the nanoparticles aggregate, resulting in a color difference ΔE > 3 and poor heat-insulating effect. Referring to Comparative Examples 2 and 4, when d > R1, the electrochromic device exhibits extremely high haze, thus the prepared electrochromic device struggles to meet the standards and achieve a satisfactory color-changing effect.

[0172] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example.

[0173] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. An ion transport layer characterized in that, Comprise: A composite nanoparticle, the composite nanoparticle comprising a thermal insulation nanoparticle and an insulating layer, the insulating layer being coated on a surface of the thermal insulation nanoparticle, wherein a thickness of the insulating layer is d, a radius of the thermal insulation nanoparticle is R1, and a radius of the composite nanoparticle is R2, the d, the R1 and the R2 satisfying: d = R2 - R1, 0 < d ≤ R1.

2. The ion transport layer of claim 1, wherein, The thermal insulation nanoparticle accounts for 2% to 5% in the ion transmission layer in terms of mass percentage.

3. The ion transport layer of claim 1, wherein, The radius R1 of the thermal insulation nanoparticle satisfies: 20 nm ≤ R1 ≤ 120 nm.

4. The ion transport layer of claim 1, wherein, The weight of the insulating layer accounts for 10% to 50% of the weight of the composite nanoparticle.

5. The ion transport layer of claim 1, wherein, The weight of the insulating layer accounts for 10% to 30% of the weight of the composite nanoparticle.

6. The ion transport layer according to any one of claims 1 to 5, wherein, The thermal insulation nanoparticle comprises at least one of nano-Cu, nano-Ag, nano-ATO, nano-ITO and nano-AZO.

7. The ion transport layer of claim 6, wherein, The insulating layer comprises at least one of a surfactant, a coupling agent or a nanodispersion.

8. The ion transport layer of claim 7, wherein, The surfactant comprises at least one of a polyether surfactant, a polyalcohol surfactant, a polyester surfactant and a polyethylene nonionic surfactant.

9. The ion transport layer of claim 8, wherein, The polyether surfactant comprises at least one of polyvinylpyrrolidone, polyethylene glycol, propylene glycol block polyether, isopropyl alcohol polyoxyalkyl ether, isomeric tridecanol random polyether, butane triol random polyether, lauryl alcohol alcohol random polyether; and / or the polyester surfactant comprises at least one of polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polybutylene succinate.

10. The ion transport layer of claim 7, wherein, The coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a phosphate coupling agent; and / or the nanodispersion comprises at least one of a nanochitosan dispersion, a nanocellulose dispersion, a nanometer aluminum sol dispersion, a nanometer silicon sol, a graphene oxide dispersion and an oxidized carbon nanotube dispersion.

11. The ion transport layer of claim 10, wherein, The silane coupling agent comprises at least one of methyl trimethoxysilane, methyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyl diethoxysilane, N-(β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane, N-(β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane, N-(β-aminoethyl-γ-aminopropyl) trimethoxysilane, 3-(methacryloyloxy) propyl trimethoxysilane, 3-(methacryloyloxy) propyl triethoxysilane, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane; and / or, The titanate coupling agent includes at least one of triisostearyl titanate isobutyl, isopropyl tri(dioctyl pyrophosphato) titanate, isopropyl tri(dodecyl benzene sulfonato) titanate, isopropyl triisostearyl titanate isobutyl, bis-triethanol amine diisopropoxy titanate, bis(acetylacetonyl) diisopropoxy titanate, bis(acetylacetonyl) ethoxy isopropoxy titanate, bis(acetylacetonyl) isobutoxy isopropoxy titanate, bis(acetyl acetic acid ethyl) diisopropoxy titanate, bis(acetyl acetic acid ethyl) diisobutoxy titanate; and / or, The aluminate coupling agent includes at least one of isopropyl di-stearoyl aluminum acid ester, aluminate coupling agent DL-411, aluminate coupling agent DL-411AF, aluminate coupling agent DL-411D, aluminate coupling agent DL-411DF; and / or, The phosphate coupling agent includes alkyl dihydrogen phosphate, ethylene methyl methacrylate phosphate, phenyl alkyl bis phosphate, phenyl phosphate.

12. The ion transport layer of claim 1, wherein, The conductive medium, the UV light curing agent and the resin are also included.

13. The ion transport layer of claim 12, wherein, The conductive medium includes an organic small molecule and a soluble conductive salt.

14. The ion transport layer of claim 13, wherein, The soluble conductive salt is an organic lithium salt, which includes at least one of 1-butyl-3-methyl imidazole hexafluorophosphate, 1-butyl-3-methyl imidazole bis(trifluoromethyl sulfonate) imide, 1-butyl-3-methyl imidazolium toluene sulfonate, 1-ethyl-2,3-dimethyl imidazole hexafluorophosphate, lithium trifluoromethane sulfonate, lithium bis-trifluoromethane sulfonimide and lithium bis-fluorosulfonimide salt; and / or, the organic small molecule includes at least one of propylene carbonate, ethylene carbonate, acetonitrile, vinyl ethylene carbonate, vinylene carbonate, N,N-dimethyl formamide, dimethyl carbonate, methyl ethyl carbonate, butanediol, propylene glycol and dimethyl propylene glycol.

15. The ion transport layer of claim 12, wherein, The UV light curing agent includes at least one of 2-hydroxy-2-methyl-1-phenyl propanone, 1-hydroxy cyclohexyl phenyl ketone, 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide and 2,4,6-trimethyl benzoyl phenyl phosphonic acid ethyl ester.

16. The ion transport layer of claim 12, wherein, The resin includes at least one of acrylate-based and polyurethane-based.

17. An electrochromic device, characterized in that, It includes: Transparent conductive layer, electrochromic layer, ion transport layer, ion storage layer and transparent conductive layer in sequence along the thickness direction, the ion transport layer is the ion transport layer according to any one of claims 1-16.

18. The electrochromic device of claim 17, wherein, The ion storage layer includes at least one of vanadium pentoxide, nickel oxide, tungsten oxide, niobium pentoxide and cerium oxide; and / or, The electrochromic layer includes at least one of poly 2,5-dibromo-3,4-ethylene dioxy thiophene, poly 3,4-ethylene dioxy thiophene, poly 3,4-bis (4-ethyl hexyloxy) thiophene, polypyrrole, polyaniline, polystyrene sulfonate, di- (2-phosphonoethyl) -4,4'-dipyridine, 1,1'-dimethyl-4,4'-dipyridine, molybdenum oxide, tungsten oxide and titanium oxide.

19. Use of an electrochromic device according to claim 17 or 18, characterized in that, The electrochromic device is used for electronic and electrical components, automobile windows, rearview mirrors and building glass windows.

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