Ion storage layer, and preparation method therefor and use thereof

Abstract

The present application relates to an ion storage layer, and a preparation method therefor and a use thereof. Based on a total mass of 100% for the ion storage layer, the ion storage layer comprises the following components in mass percentage: an antioxidant: ≤10%, a light stabilizer: ≤10%, a heat stabilizer: ≤10%, another auxiliary agent: ≤10%, and an ion storage layer basic component: the remaining percentage to 100%. At least one of the mass percentage of the antioxidant, the mass percentage of the light stabilizer, and the mass percentage of the heat stabilizer is not 0%; the ion storage layer basic component comprises at least one of an organic material and an inorganic material. The ion storage layer provided by the present application has good stability, and still has good ion storage performance after long-term illumination and repeated cycles. An electrochromic film prepared from the ion storage layer provided by the present application solves the technical problems in related art of unstable electrochromic devices and the like, and has the advantages of being stable, achieving a good color-change effect, and having long service life.

Description

Ion storage layer and its preparation method and application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application with application number 202311857462.0 filed with the Chinese Patent Office on December 29, 2023, entitled “A kind of ion storage layer, its preparation method and application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present application belongs to the field of electrochromic technology, and in particular relates to an ion storage layer and a preparation method and application thereof. Background Art

[0004] An electrochromic device includes a first and second conductive substrate layers positioned opposite each other, and an electrochromic layer structure disposed between the first and second conductive substrate layers. When a voltage is applied to the first and second conductive substrate layers, the electrochromic layer structure undergoes a reversible and stable color change in response to the voltage across the first and second conductive substrate layers. Therefore, the characteristics of electrochromic devices can be utilized to create smart devices with adjustable optical ranges.

[0005] The electrochromic devices in related technologies will experience significant degradation in various parameters after multiple cycles or long periods of exposure to light, especially the performance degradation of the ion storage layer. Summary of the Invention

[0006] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0007] The present application provides an ion storage layer, a preparation method and application thereof. The electrochromic device formed by the ion storage layer has the advantages of good cycle performance and long life.

[0008] In a first aspect, the present application provides an ion storage layer. Taking the total mass of the ion storage layer as 100%, the ion storage layer includes the following components in terms of mass percentage:

[0009] wherein at least one of the mass percentage of the antioxidant, the mass percentage of the light stabilizer, and the mass percentage of the heat stabilizer is not 0%;

[0010] The ion storage layer basic component includes at least one of an organic material and an inorganic material.

[0011] In the present application, at least one of an antioxidant, a light stabilizer, and a heat stabilizer, as well as other auxiliary agents, is added to the ion storage layer. At least one of the antioxidant, light stabilizer, and heat stabilizer is used as a stabilizer, so that the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated embedding and de-embedding of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved. The ion storage layer can ensure that ions and electrons can smoothly transition from other layers to the ion storage layer under long-term exposure to light and multiple cycles, thereby ensuring the durability of the performance of the ion storage layer, thereby ensuring the color change speed and transmittance adjustable range of the electrochromic device. In addition, the ion storage layer in the present application always maintains a firm bond with the other layers and will not fall off from the other layers, thereby maintaining good color change performance; thereby improving the stability and color change performance of the entire electrochromic device. The electrochromic film made of the ion storage layer described in this application solves technical problems in related technologies such as instability of electrochromic devices due to performance degradation of the ion storage layer, and has the advantages of stable and good color changing effect and long life.

[0012] Preferably, the mass percentage of the antioxidant is ≤10% and not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0013] Preferably, the mass percentage of the light stabilizer is ≤10% and not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0014] Preferably, the mass percentage of the heat stabilizer is ≤10% and not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0015] Preferably, the mass percentage of the other auxiliary agents is ≤10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0016] Preferably, the total mass of the antioxidant, light stabilizer and heat stabilizer accounts for 0.5%-20% of the total mass of the ion storage layer.

[0017] Illustratively, the sum of the masses of the antioxidant, light stabilizer and heat stabilizer accounts for 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16% or 18% of the total mass of the ion storage layer.

[0018] Preferably, after mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is in the range of: -50 to 50; and the b* value is in the range of: -60 to 60.

[0019] For example, the a* value defined in the Lab color space ranges from -50 to 50, which can be -45, -40, -30, -20, -10, 0, 10, 20, 30, 40 or 45, etc.; the b* value ranges from -60 to 60, which can be -55, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50 or 55, etc.

[0020] Preferably, the antioxidant has an a* value defined by the Lab color space in the range of -15 to 15, and a b* value in the range of -35 to 35.

[0021] For example, the a* value of the antioxidant defined by the Lab color space can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12 or 14, etc., and the b* value range of -35 to 35 can be -30, -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25 or 30, etc.

[0022] Preferably, the antioxidant comprises at least one of a free radical absorber, a metal ion chelator and a singlet oxygen quencher, wherein typical but non-limiting combinations include: a combination of a free radical absorber and a metal ion chelator, a combination of a metal ion chelator and a singlet oxygen quencher, a combination of a free radical absorber, a metal ion chelator and a singlet oxygen quencher, and the like.

[0023] Preferably, the free radical absorber includes at least one of butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone, ferrous sulfate and tocopherol, wherein typical but non-limiting combinations of the free radical absorber include: a combination of butylated hydroxyanisole and 2,6-di-tert-butyl-4-methylphenol, a combination of 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone and tocopherol, a combination of butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone and tocopherol, and the like.

[0024] Preferably, the metal ion chelating agent comprises at least one of ethylenediaminetetraacetic acid (EDTA), citric acid, polyphosphoric acid and phytic acid, wherein typical but non-limiting combinations of the metal ion chelating agent include: a combination of ethylenediaminetetraacetic acid and citric acid, a combination of citric acid, polyphosphoric acid and phytic acid, a combination of ethylenediaminetetraacetic acid, citric acid, polyphosphoric acid and phytic acid, etc.

[0025] Preferably, the singlet oxygen quencher comprises at least one of benzidine, diphenylamine and β-carotene, wherein typical but non-limiting combinations of the singlet oxygen quencher include: a combination of benzidine and diphenylamine, a combination of diphenylamine and β-carotene, a combination of benzidine, diphenylamine and β-carotene, and the like.

[0026] Preferably, the light stabilizer has an a* value range of -15 to 50 and a b* value range of -30 to 30 as defined by the Lab color space. Exemplarily, the a* value range of -15 to 50 of the light stabilizer as defined by the Lab color space may be -13, -12, -10, -8, -6, -4, -2, 0, 10, 20, 25, 30, 35, 40, or 45, etc.; the b* value range of -30 to 30 may be -28, -26, -24, -20, -18, -15, -10, -8, -5, 0, 5, 10, 12, 15, 18, 20, 22, 25, or 28, etc.

[0027] Preferably, the light stabilizer includes at least one of a light shielding agent, an ultraviolet absorber and a free radical scavenger.

[0028] Preferably, the light shielding agent includes at least one of titanium dioxide, zinc oxide and carbon black.

[0029] Preferably, the ultraviolet absorber includes at least one of phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

[0030] Preferably, the free radical scavenger includes at least one of 2,2,6,6-tetramethylpiperidinyl oxide, dibutylhydroxytoluene and 1,1-diphenylethylene, wherein typical but non-limiting combinations of the free radical scavenger include: a combination of 2,2,6,6-tetramethylpiperidinyl oxide and dibutylhydroxytoluene, a combination of dibutylhydroxytoluene and 1,1-diphenylethylene, a combination of 2,2,6,6-tetramethylpiperidinyl oxide, dibutylhydroxytoluene and 1,1-diphenylethylene, and the like.

[0031] Preferably, the thermal stabilizer has an a* value range of -15 to 15 and a b* value range of -30 to 30 defined by the Lab color space, wherein -15 to 15 may be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12 or 14, etc.; -30 to 30 may be -25, -20, -15, -10, -5, 0, 5, 10, 15, 20 or 25, etc.

[0032] Preferably, the thermal stabilizer includes at least one of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer and a Group IIA metal stabilizer, wherein typical but non-limiting combinations of the thermal stabilizer include: a combination of a tin stabilizer and a lead stabilizer, a combination of a lead stabilizer, a mixed metal stabilizer and a Group IIA metal stabilizer, a combination of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer and a Group IIA metal stabilizer, and the like.

[0033] Preferably, the heat stabilizer comprises tribasic sulfate and / or calcium stearate.

[0034] Preferably, the tribasic sulfate includes tribasic sodium sulfate and / or tribasic lead sulfate.

[0035] Preferably, the other additives include at least one of a leveling agent, a defoaming agent and a dispersant, wherein typical but non-limiting combinations include: a combination of a leveling agent and a defoaming agent, a combination of a defoaming agent and a dispersant, a combination of a leveling agent, a defoaming agent and a dispersant, and the like.

[0036] Preferably, the basic components of the ion storage layer include at least one of metal oxide, a dopant of metal oxide and an organic polymer.

[0037] Preferably, the ion storage layer comprises at least one of a metal oxide and a dopant of the metal oxide.

[0038] Preferably, among the basic components of the ion storage layer, the metal oxide includes at least one of nickel oxide, vanadium oxide, titanium oxide, tungsten trioxide (WO3) and niobium oxide, wherein typical but non-limiting combinations of the basic components of the ion storage layer include: a combination of nickel oxide and vanadium oxide, a combination of titanium oxide, tungsten trioxide and niobium oxide, a combination of nickel oxide, vanadium oxide, titanium oxide, tungsten trioxide and niobium oxide, etc.

[0039] Exemplarily, the nickel oxide includes nickel monoxide (NiO).

[0040] For example, the vanadium oxide has the molecular formula VO x , wherein the value of x satisfies the valence, such as vanadium monoxide, vanadium trioxide, vanadium dioxide or vanadium pentoxide.

[0041] Illustratively, the titanium oxide includes titanium dioxide (TiO 2 ) and / or titanium oxide (TiO).

[0042] For example, the niobium oxide has the molecular formula NbO x , wherein the value of x satisfies the valence, such as niobium monoxide, niobium dioxide, niobium trioxide or niobium pentoxide.

[0043] Preferably, the dopant of the metal oxide includes tantalum-doped titanium dioxide and / or niobium-doped indium dioxide.

[0044] Preferably, the organic polymer includes at least one of triphenylamine polymer, polythiophene and polypyrrole, wherein typical but non-limiting combinations of the organic polymer include: a combination of triphenylamine polymer and polythiophene, a combination of polythiophene and polypyrrole, a combination of triphenylamine polymer, polythiophene and polypyrrole, etc.

[0045] Preferably, the basic components of the ion storage layer further include a binder and a surfactant, and the mass of the binder accounts for ≤5% of the total mass of the ion storage layer.

[0046] Illustratively, the mass of the adhesive accounts for 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5% of the total mass of the ion storage layer; the mass of the surfactant accounts for ≤3% of the total mass of the ion storage layer, for example, 0.2%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.3%, 2.5% or 2.8%; the specific type and addition amount can be selected according to actual needs.

[0047] In a second aspect, the present application provides a method for preparing the ion storage layer according to the first aspect, the method comprising the following steps:

[0048] The antioxidant, light stabilizer, heat stabilizer, other additives and basic components of the ion storage layer are weighed in preset mass percentages, mixed to obtain a mixture, and then the mixture is coated on the conductive surface of the conductive base layer to obtain the ion storage layer.

[0049] Preferably, the preset mass percentages are antioxidant ≤10%, light stabilizer ≤10%, heat stabilizer ≤10%, other additives ≤10% and basic components of the ion storage layer to 100%; wherein, at least one of the mass percentage of the antioxidant, the mass percentage of the light stabilizer and the mass percentage of the heat stabilizer is not 0%.

[0050] Preferably, the coating method includes magnetron sputtering or wet coating.

[0051] Preferably, the wet coating comprises spin coating.

[0052] In a third aspect, the present application provides an electrochromic film, which includes an ion storage layer, an electrolyte layer, and an electrochromic layer stacked in sequence, wherein the ion storage layer is the ion storage layer as described in the first aspect.

[0053] In the present application, the selection of antioxidants, light stabilizers and heat stabilizers in the ion storage layer is related to the basic components of the ion storage layer. By adding antioxidants, light stabilizers, heat stabilizers and other additives to the ion storage layer, the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated embedding and de-embedding of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, which can ensure that ions and electrons can smoothly jump from other layers to the ion storage layer under long-term exposure to light and multiple cycles, thereby ensuring the color change speed and adjustable range of the transmittance of the electrochromic device.

[0054] In addition, when forming the electrochromic film, it is also necessary to select a stabilizing additive with a complementary color according to the color of the electrochromic layer material. For example, when the electrochromic material layer is blue in the dark state, the b* of the electrochromic material layer is <0. The overall color of the electrochromic device can be made brighter by adding a yellow antioxidant with b*>0, such as butylated hydroxyanisole, a yellow light stabilizer, such as 2,4,6-tris(2'-n-butoxyphenyl)-1,3,5-triazine, or a yellow heat stabilizer. Close to neutral; when the electrochromic material layer is reddish, at this time the a* of the electrochromic material layer is greater than 0, the overall color of the electrochromic device can be made close to neutral by adding a green antioxidant with a*<0, a green light stabilizer, such as: 2,2'-thiobis(4-tert-octylphenoloxy)nickel, or a green heat stabilizer; preferably, the specific added content does not exceed 20% to avoid the color of the electrochromic device being affected by the additive in the transparent state and showing the color of the additive, which affects the user's visual effect.

[0055] The conductive substrate described in the present application includes a transparent substrate layer and a transparent conductive layer, the transparent conductive layer is arranged on one side of the substrate layer, and the ion storage layer is arranged on the side of the transparent conductive layer facing away from the substrate layer; the transparent substrate layer includes but is not limited to: glass, organic glass and flexible substrates such as polyethylene terephthalate (PET) film, polycarbonate (PC) film, etc.; the conductive layer includes conductive oxides such as ITO, IZO, etc.

[0056] In a fourth aspect, the present application provides an electrochromic device, which includes the electrochromic film described in the third aspect.

[0057] In a fifth aspect, the present application provides a terminal product, which includes at least one of the ion storage layer as described in the first aspect, the electrochromic membrane as described in the third aspect, and the electrochromic device as described in the fourth aspect, wherein the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, an electronic product housing, glasses, a vehicle, or a display panel.

[0058] Compared with the related art, this application has the following beneficial effects:

[0059] The electrochromic device formed by the ion storage layer provided in the present application has a significantly longer lifespan than the electrochromic devices of the related art because the ion storage layer includes at least one of an antioxidant, a light stabilizer and a heat stabilizer. During use, the color change speed is not easy to decline, and the color change range is maintained for a longer time, which has the effect of significantly improving the lifespan.

[0060] Still other aspects will become apparent upon reading and understanding the detailed description. DETAILED DESCRIPTION

[0061] The technical solution of the present application is further described below through specific implementation methods. It should be noted that, as long as no conflict is constituted, the various embodiments in the present application and the various features in the embodiments can be combined with each other, and the resulting technical solutions are all within the scope of protection of the present application. It should be understood by those skilled in the art that the embodiments are merely to help understand the present application and should not be regarded as specific limitations of the present application.

[0062] The inventors have carefully studied and found that after multiple cycles or long periods of exposure to light, the electrochromic device will experience a narrowing of the color change endpoint range or a slowing of the color change speed, and other phenomena such as reduced color change performance. One of the reasons for the reduced color change performance is that some components of the ion storage layer (such as adhesives or surfactants, etc.) will age and fail after being exposed to long-term light or multiple cycles of charge and discharge of the device. Although the basic components of the ion storage layer still have the function of ion storage, the failure of some components (such as adhesives or surfactants, etc.) after exposure to light will cause the wettability and adhesion of the ion storage layer to other layers to deteriorate, thereby reducing the transition of ions or electrons from other layers to the ion storage layer, resulting in an increase in the internal resistance of the entire device, which in turn causes the entire device to experience a reduction in color change speed, a narrowing of the adjustable transmittance range, and other performance degradations. It may even cause the ion storage layer to have low adhesion to other layers and fall off and separate from other layers, ultimately causing the entire electrochromic device to lose its color change and dimming functions.

[0063] In view of the above problems, the first aspect of the present application provides an ion storage layer. Taking the total mass of the ion storage layer as 100%, the ion storage layer includes the following components in terms of mass percentage:

[0064] wherein at least one of the mass percentage of the antioxidant, the mass percentage of the light stabilizer, and the mass percentage of the heat stabilizer is not 0%;

[0065] The ion storage layer basic component includes at least one of an organic material and an inorganic material.

[0066] In the embodiment of the present application, at least one of an antioxidant, a light stabilizer, and a heat stabilizer, as well as other additives, is added to the ion storage layer. At least one of the antioxidant, light stabilizer, and heat stabilizer is used as a stabilizer, so that the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated insertion and removal of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved. The ion storage layer can ensure that ions and electrons can smoothly transition from other layers to the ion storage layer under long-term exposure to light and multiple cycles, ensuring the durability of the performance of the ion storage layer, thereby ensuring the color change speed and transmittance adjustable range of the electrochromic device. In addition, the ion storage layer in the present application always maintains a firm bond with the other layers and will not fall off from the other layers, maintaining good color change performance; thereby improving the stability and color change performance of the entire electrochromic device. The electrochromic film made of the ion storage layer described in the embodiment of the present application solves technical problems in related technologies such as instability of electrochromic devices due to performance degradation of the ion storage layer, and has the advantages of stable and good color changing effect and long life.

[0067] Illustratively, the mass percentage of the antioxidant is ≤10% and is not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0068] Illustratively, the mass percentage of the light stabilizer is ≤10% and not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0069] Illustratively, the mass percentage of the thermal stabilizer is ≤10% and is not equal to 0%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0070] Illustratively, the mass percentage of the other additives is ≤10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0071] In the present application, the mass percentages of the antioxidant, light stabilizer, heat stabilizer and other additives are each independently preferably ≤10%. The reason is that the mass percentages of the antioxidant, light stabilizer, heat stabilizer and other additives are all controlled within 10%, which can avoid the excessive content of the basic components of the non-ionic storage layer and the weakening of the ability of the ion storage layer to store ions. In addition, the antioxidant, light stabilizer and heat stabilizer are all stabilizing additives for the ion storage layer. Different stabilizing additives can be selected for different devices used in different environments. For example, when the indoor ambient light is not strong, an antioxidant or a heat stabilizer can be added. When used in electrochromic devices such as curtain walls and car skylights that are exposed to outdoor environments for a long time, a light stabilizer can be added as the main stabilizing additive. Of course, antioxidants, light stabilizers and heat stabilizers can also be mixed as stabilizing additives.

[0072] Exemplarily, the sum of the masses of the antioxidant, light stabilizer and heat stabilizer accounts for 0.5%-20% of the total mass of the ion storage layer, for example, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16% or 18%, etc.

[0073] In the present application, the sum of the mass of the antioxidant, light stabilizer, and heat stabilizer is controlled to be within 20% of the total mass of the ion storage layer. The reason is that the sum of the mass percentages of the antioxidant, light stabilizer, and heat stabilizer should not be controlled too high. If the sum of the mass percentages of the antioxidant, light stabilizer, and heat stabilizer is too high, the mass percentages of the basic components of the ion storage layer will be relatively reduced, thereby affecting the ion storage capacity of the ion storage layer. If the sum of the mass percentages of the antioxidant, light stabilizer, and heat stabilizer is too low, the stability of the ion storage layer cannot be guaranteed. Therefore, the content of the additives needs to be set within a relatively appropriate range to ensure the ion storage capacity while also improving the stability of the ion storage layer, thereby increasing the service life of the electrochromic device. Specifically, the specific component content of the antioxidant, light stabilizer, and heat stabilizer is determined according to the specific composition of the ion storage layer. Preferably, the sum of the mass of the oxidant, light stabilizer, and heat stabilizer accounts for 0.5%-10% of the total mass of the ion storage layer.

[0074] Exemplarily, the range of a* values ​​defined by the Lab color space after mixing the components other than the basic components of the ion storage layer is: -50 to 50; and the range of b* values ​​is: -60 to 60, wherein -50 to 50 can be -45, -40, -30, -20, -10, 0, 10, 20, 30, 40 or 45, etc.; -60 to 60 can be -55, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50 or 55, etc.

[0075] In the present application, in the three-layer structure of the electrochromic film of the related art, the ion storage layer is usually colorless, and the electrolyte layer is also colorless, but the electrochromic layer is colored, usually bluish or greenish, resulting in the electrochromic film's color change endpoint, especially the dark state color change endpoint, being blue or green. The present application adds an ion storage layer that can complement the color of the electrochromic layer, so that the electrochromic film maintains a neutral or near-neutral color during the color change process or at the dark state color change endpoint, thereby improving the consistency of the appearance.

[0076] In this application, "neutral" color means: when the Lab a* and b* values ​​are equal to 0, the color effect is neutral, i.e., colorless (neutral color). When the Lab a* and b* values ​​tend toward 0, the color effect is close to neutral. A color effect that is neutral or close to neutral is more visually friendly.

[0077] It should be noted that the L* value, a* value, and b* value in the Lab color space represent the brightness, red-green color, and yellow-blue color, respectively. The Lab value includes the a* value and the b* value. The larger the L* value, the higher the brightness of the color. When a*>0, it means that the color is red, and the larger the a* value, the more reddish the color; when a*<0, it means that the color is green, and the smaller the a* value, the more greenish the color. When b*>0, it means that the color is yellow, and the larger the b* value, the more yellowish the color; when b*<0, it means that the color is blue, and the smaller the b* value, the more bluish the color. Color parameters: L* value (Lightness) is between 0 and 100, with 0 representing black and 100 representing white; a* value (Redness) represents the color between red and green, with 100 being red and -80 being green; b* value (Yellowness) represents the color between yellow and blue, with 100 being yellow and -80 being blue. The closer the a* value and b* value are to 0, the closer the color is to neutral, and the more comfortable it is for the human eye. The L* value is the change in transmittance caused by the voltage applied to the electrochromic device; for example, the electrochromic device changes its transmittance due to the voltage applied at both ends. When the electrochromic device responds to the voltage and changes color to a transmittance of 100%, the L* value is 100. If the transmittance of the electrochromic device is 0%, the corresponding L* value is 0. The range of the adjustable transmittance of the electrochromic device is affected by the material of the electrochromic layer.

[0078] In the embodiments of the present application, the electrochromic device changes its transmittance by applying a voltage to the two conductive layers of the device to change its own color. The electrochromic device usually switches between a colored state, an intermediate state, and a transparent state. The colored states include green, black, blue, red, etc. In the related art, when the electrochromic device switches between any two states of the colored state, the intermediate state, and the transparent state, or when it reaches the end of the color change, the color of the electrochromic device is blue at the end of the color change or green during the color change process, causing visual discomfort to the user. Furthermore, in the related art, the reason why the color of the electrochromic device during the color change process causes visual discomfort is that the electrochromic material layer is usually colored, while the ion storage layer and the electrolyte layer are usually colorless. However, due to the material properties of the electrochromic material layer, it is difficult to control the electrochromic material layer to a neutral or near-neutral color. Therefore, in this application, a trace amount of stabilizing additive is added to the ion storage layer, and the Lab value of the added stabilizing additive is adjusted to adjust the color state of the electrochromic device during the color change process and at the end of the color change. While ensuring that the material properties of the electrochromic material layer are not changed, the addition of a colored stabilizing additive can improve the stability of the device, and at the same time make the entire color change process of the electrochromic device neutral or close to neutral, which is closer to the human visual effect and improves the comfort level without causing visual impact to the user and reducing the user's experience.

[0079] Exemplarily, the antioxidant has an a* value defined by the Lab color space in the range of -15 to 15; a b* value in the range of -35 to 35, wherein -15 to 15 may be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12 or 14, etc.; and -35 to 35 may be -30, -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25 or 30, etc.

[0080] In the present application, the a* value range defined in the Lab color space of the antioxidant is preferably: -15 to 15; the b* value range is preferably: -30 to 30. The reason is that an antioxidant with a certain color is selected, and the a* value and b* value of the antioxidant are selected to be close to the neutral color, so that the ion storage layer has a color that matches the electrochromic layer, and then matches the electrochromic material layer of the electrochromic device, so that the color of the electrochromic device is closer to the neutral color during the color change process or at the end of the color change, which can better meet the user's visual needs and enhance the user experience. In addition, the addition of antioxidants can also improve the stability of the ion storage layer and ensure the service life of the electrochromic device. In addition, by adjusting the specific proportion of the added antioxidants and selecting antioxidants with colors close to neutral, the initial color of the entire device will not be affected when a small amount of antioxidants is added, ensuring the appearance of the electrochromic device in the faded state, avoiding the non-neutral color of the faded electrochromic device, and further meeting the user's visual needs.

[0081] Exemplarily, the antioxidant includes at least one of a free radical absorber, a metal ion chelator and a singlet oxygen quencher, wherein typical but non-limiting combinations include: a combination of a free radical absorber and a metal ion chelator, a combination of a metal ion chelator and a singlet oxygen quencher, a combination of a free radical absorber, a metal ion chelator and a singlet oxygen quencher, and the like.

[0082] Exemplarily, the free radical absorber includes at least one of butylated hydroxyanisole, antioxidant BHT, tert-butylhydroquinone, ferrous sulfate and tocopherol, wherein typical but non-limiting combinations include: a combination of butylated hydroxyanisole and 2,6-di-tert-butyl-4-methylphenol, a combination of 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone and tocopherol, a combination of butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone and tocopherol, and the like.

[0083] Exemplarily, the metal ion chelating agent includes at least one of ethylenediaminetetraacetic acid, citric acid, polyphosphoric acid and phytic acid, wherein typical but non-limiting combinations include: a combination of ethylenediaminetetraacetic acid and citric acid, a combination of citric acid, polyphosphoric acid and phytic acid, a combination of ethylenediaminetetraacetic acid, citric acid, polyphosphoric acid and phytic acid, and the like.

[0084] Illustratively, the singlet oxygen quencher includes at least one of benzidine, diphenylamine, and β-carotene, wherein typical but non-limiting combinations include: a combination of benzidine and diphenylamine, a combination of diphenylamine and β-carotene, a combination of benzidine, diphenylamine, and β-carotene, and the like.

[0085] Illustratively, the light stabilizer has an a* value range of -15 to 50 and a b* value range of -30 to 30 defined by the Lab color space, wherein -15 to 50 may be -13, -12, -10, -8, -6, -4, -2, 0, 10, 20, 25, 30, 35, 40 or 45, etc.; -30 to 30 may be -28, -26, -24, -20, -18, -15, -10, -8, -5, 0, 5, 10, 12, 15, 18, 20, 22, 25 or 28, etc.

[0086] In the present application, the a* value range of the light stabilizer defined by the Lab color space is preferably: -15 to 50, and the b* value range is preferably: -30 to 30. The reason is that the wider Lab value range can meet the color matching of a wider range of colors, so that the ion storage layer can adapt to more different colors of electrochromic layers. In addition, electrochromic devices are used in relatively harsh environments, such as long-term exposure to the sun, which can easily accelerate the aging speed and make the device itself yellow. The wider color range of the ion storage layer can meet the complementary color of the aging discoloration of the device, so that the color of the electrochromic device is close to neutral throughout its life cycle, reducing the possibility of the electrochromic device being eliminated due to the color affecting the appearance, and further improving the service life of the electrochromic device. Furthermore, by selecting a light stabilizer with a* and b* values ​​within a certain range, and the a* and b* values ​​of the light stabilizer within this range can also block some blue-violet light, it helps to improve the light resistance of the electrochromic device, while reducing the impact of blue-violet light on the stability of the electrochromic device, thereby improving the stability of the electrochromic device.

[0087] Illustratively, the light stabilizer includes at least one of a light shielding agent, an ultraviolet absorber, and a free radical scavenger.

[0088] Illustratively, the light shielding agent includes at least one of titanium dioxide, zinc oxide, and carbon black.

[0089] Illustratively, the ultraviolet absorber includes at least one of phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.

[0090] Exemplarily, the free radical scavenger includes at least one of 2,2,6,6-tetramethylpiperidinyl oxide, dibutylhydroxytoluene and 1,1-diphenylethylene, wherein typical but non-limiting combinations include: a combination of 2,2,6,6-tetramethylpiperidinyl oxide and dibutylhydroxytoluene, a combination of dibutylhydroxytoluene and 1,1-diphenylethylene, a combination of 2,2,6,6-tetramethylpiperidinyl oxide, dibutylhydroxytoluene and or 1,1-diphenylethylene, and the like.

[0091] Exemplarily, the a* value range of the thermal stabilizer defined by the Lab color space is: -15 to 15, and the b* value range is: -30 to 30, wherein -15 to 15 can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12 or 14, etc.; -30 to 30 can be -25, -20, -15, -10, -5, 0, 5, 10, 15, 20 or 25, etc.

[0092] In the present application, the a* value range of the thermal stabilizer defined by the Lab color space is preferably: -15 to 15, and the b* value range is preferably: -30 to 30. The reason is that: a thermal stabilizer with a certain color is selected, and the a* value and b* value of the selected thermal stabilizer are close to the neutral color, so that the ion storage layer has a color that matches the electrochromic layer, and then matches the electrochromic material layer of the electrochromic device, so that the electrochromic device is in the color change process or at the end of the color change, especially at the dark end, its color is closer to the neutral color, which can better meet the user's visual needs and enhance the user experience. In addition, the addition of the thermal stabilizer can also play a role in improving the stability of the ion storage layer and ensuring the service life of the electrochromic device. In addition, by adjusting the specific proportion of the thermal stabilizer added and selecting a thermal stabilizer with a color close to neutral, the initial color of the entire device is not affected when a small amount of thermal stabilizer is added, ensuring the appearance of the electrochromic device in the faded state, avoiding the non-neutral color of the faded electrochromic device, and further meeting the user's visual needs.

[0093] Exemplarily, the thermal stabilizer includes at least one of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer, wherein typical but non-limiting combinations include: a combination of a tin stabilizer and a lead stabilizer, a combination of a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer, a combination of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer, and the like.

[0094] Illustratively, the heat stabilizer includes tribasic sulfate and / or calcium stearate.

[0095] Illustratively, the tribasic sulfate includes tribasic sodium sulfate and / or tribasic lead sulfate.

[0096] Exemplarily, the other additives include at least one of a leveling agent, a defoaming agent and a dispersant, wherein typical but non-limiting combinations include: a combination of a leveling agent and a defoaming agent, a combination of a defoaming agent and a dispersant, a combination of a leveling agent, a defoaming agent and a dispersant, and the like.

[0097] For example, the leveling agent includes polydimethylsiloxane and / or dioctyl phthalate; the defoaming agent includes sodium tripolyphosphate; and the dispersant includes tetraethyl silicate and / or polyoxyethylene oxypropylene glycerol. The other auxiliary agents include any one or a combination of at least two of polydimethylsiloxane, dioctyl phthalate, polyoxyethylene oxypropylene glycerol, sodium tripolyphosphate, or tetraethyl silicate. Typical but non-limiting combinations include: a combination of polydimethylsiloxane and sodium tripolyphosphate, a combination of sodium tripolyphosphate and tetraethyl silicate, and a combination of polydimethylsiloxane, sodium tripolyphosphate, and tetraethyl silicate.

[0098] In one embodiment of the present application, the leveling properties of the ion storage layer are adjusted by adding a leveling agent, resulting in a high leveling effect when the ion storage layer is applied to a conductive substrate, making the thickness of the ion storage layer more uniform. Furthermore, the addition of a defoaming agent reduces the generation of foam during agitation of the ion storage layer. In one embodiment of the present application, the addition of a dispersant further evenly disperses the components of the ion storage layer, ensuring uniform ion storage capacity and stability at all points in the ion storage layer, thereby improving the stability of the electrochromic device.

[0099] Exemplarily, the basic components of the ion storage layer include at least one of metal oxide, a dopant of metal oxide, and an organic polymer.

[0100] In the embodiment of the present application, the basic component of the ion storage layer is preferably at least one of a metal oxide, a dopant of a metal oxide and an organic polymer. The reason is that it has a high ion storage capacity. Regardless of whether it is an organic system or an inorganic system, the improvement of the ion storage layer provided in the present application can ensure the original ion storage capacity of the ion storage layer while ensuring the stability of the ion storage layer, thereby improving the stability of the ion storage layer and thus improving the service life of the electrochromic device.

[0101] Exemplarily, the basic components of the ion storage layer include at least one of metal oxide and metal oxide dopants. The metal oxide or the metal oxide has a high ion storage capacity, and its cycle number can reach tens of thousands of cycles, further improving the service life of the electrochromic device. Typical but non-limiting combinations include: a combination of metal oxide and metal oxide dopants, a combination of metal oxide dopants and organic polymers, a combination of metal oxide, metal oxide dopants and organic polymers, etc.

[0102] Exemplarily, among the basic components of the ion storage layer, the metal oxide includes at least one of nickel oxide, vanadium oxide, titanium oxide, tungsten trioxide and niobium oxide, wherein typical but non-limiting combinations include: a combination of nickel oxide and vanadium oxide, a combination of titanium oxide, tungsten trioxide and niobium oxide, a combination of nickel oxide, vanadium oxide, titanium oxide, tungsten trioxide and niobium oxide, etc.

[0103] In the embodiment of the present application, the ion storage layer of the inorganic metal oxide has a high ion storage capacity. At the same time, it can be prepared in a relatively low temperature environment, reducing the harshness of the production conditions, so that the ion storage layer can be prepared in a low temperature environment without the need for a high temperature environment, thereby reducing the loss of activity of antioxidants, light stabilizers and heat stabilizers caused by high-temperature preparation, thereby improving the service life of the ion storage layer.

[0104] Illustratively, the nickel oxide includes nickel monoxide.

[0105] For example, the vanadium oxide has the molecular formula VO x , wherein the value of x satisfies the valence, such as vanadium monoxide, vanadium trioxide, vanadium dioxide or vanadium pentoxide.

[0106] Illustratively, the titanium oxide includes titanium dioxide and / or titanium oxide.

[0107] For example, the niobium oxide has the molecular formula NbO x , wherein the value of x satisfies the valence, such as niobium monoxide, niobium dioxide, niobium trioxide or niobium pentoxide.

[0108] Exemplarily, the dopant of the metal oxide includes tantalum-doped titanium dioxide and / or niobium-doped indium dioxide.

[0109] Exemplarily, the organic polymer includes at least one of triphenylamine polymer, polythiophene and polypyrrole, wherein typical but non-limiting combinations include: a combination of triphenylamine polymer and polythiophene, a combination of polythiophene and polypyrrole, a combination of triphenylamine polymer, polythiophene and polypyrrole, and the like.

[0110] Exemplarily, the basic components of the ion storage layer also include an adhesive and a surfactant, and the mass of the adhesive accounts for ≤5% of the total mass of the ion storage layer, for example, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, etc.; the mass of the surfactant accounts for ≤3% of the total mass of the ion storage layer, for example, 0.2%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.3%, 2.5% or 2.8%, etc.; the specific type and addition amount can be selected according to actual needs.

[0111] In the embodiments of the present application, adhesives and surfactants are added to improve the adhesion between the ion storage layer and other layers. At the same time, the Lab values ​​of selected antioxidants, light stabilizers, or heat stabilizers are adjusted to improve the effect of the addition of adhesives and surfactants on the device color. This ensures that the electrochromic device, after the addition of adhesives and surfactants, is more comfortable to the human eye and improves the user experience. The ion storage layer can be formed with excellent overall performance based on the addition of adhesives and surfactants.

[0112] In a second aspect, the present application provides a method for preparing the ion storage layer according to the first aspect, the method comprising the following steps:

[0113] The antioxidant, light stabilizer, heat stabilizer, other additives and basic components of the ion storage layer are weighed in preset mass percentages, mixed to obtain a mixture, and then the mixture is coated on the conductive surface of the conductive base layer to obtain the ion storage layer.

[0114] Preferably, the mass percentages are antioxidant ≤ 10%, light stabilizer ≤ 10%, heat stabilizer ≤ 10%, other additives ≤ 10% and basic components of the ion storage layer up to 100%; wherein, at least one of the mass percentages of the antioxidant, the mass percentage of the light stabilizer and the mass percentage of the heat stabilizer is not 0%.

[0115] Preferably, the coating method includes magnetron sputtering or wet coating.

[0116] Preferably, the wet coating comprises spin coating.

[0117] In a third aspect, the present application provides an electrochromic film, which includes an ion storage layer, an electrolyte layer, and an electrochromic layer stacked in sequence, wherein the ion storage layer is the ion storage layer as described in the first aspect.

[0118] In the present application, the selection of antioxidants, light stabilizers and heat stabilizers in the ion storage layer is related to the basic components of the ion storage layer. By adding antioxidants, light stabilizers, heat stabilizers and other additives to the ion storage layer, the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated embedding and de-embedding of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, and the ion storage layer can ensure that ions and electrons smoothly jump from other layers to the ion storage layer under long-term exposure to light and multiple cycles, thereby ensuring the color change speed and adjustable range of the transmittance of the electrochromic device.

[0119] In addition, when forming the electrochromic film, it is also necessary to select a stabilizing additive with a complementary color according to the color of the electrochromic layer material. For example, when the electrochromic material layer is blue in the dark state, the b* of the electrochromic material layer is <0. A yellow antioxidant with b*>0, such as butylated hydroxyanisole, a yellow light stabilizer, such as 2,4,6-tris(2'-n-butoxyphenyl)-1,3,5-triazine, or a yellow heat stabilizer can be added to make the overall color of the device closer to neutral. When the electrochromic material layer is reddish, the a* of the electrochromic material layer is >0. A green antioxidant with a*<0, a green light stabilizer, such as 2,2'-thiobis(4-tert-octylphenoloxy)nickel, or a green heat stabilizer can be added to make the overall color of the device closer to neutral. Preferably, the specific added content does not exceed 20% to avoid the color of the device being affected by the additive in the transparent state and showing the color of the additive, which affects the user's visual effect.

[0120] The conductive substrate described in the embodiment of the present application includes a transparent substrate layer and a transparent conductive layer, the transparent conductive layer is arranged on one side of the substrate layer, and the ion storage layer is arranged on the side of the transparent conductive layer facing away from the substrate layer; the transparent substrate layer includes but is not limited to: glass, organic glass and flexible substrates such as PET film, PC film, etc.; the conductive layer includes conductive oxides such as ITO, IZO, etc.

[0121] In a fourth aspect, the present application provides an electrochromic device, which includes the electrochromic film described in the third aspect.

[0122] In a fifth aspect, the present application provides a terminal product, which includes at least one of the ion storage layer as described in the first aspect, the electrochromic membrane as described in the third aspect, and the electrochromic device as described in the fourth aspect, wherein the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, an electronic product housing, glasses, a vehicle, or a display panel.

[0123] The basic components of the ion storage layer described in this application can be organic or inorganic materials, which allows for a wider range of material matching. The electrochromic layer formed by the ion storage layer and organic or inorganic electrochromic materials further forms an electrochromic device with a long life. Preferably, by adding colored antioxidants, heat stabilizers, light stabilizers, etc., the ion storage layer can be adapted to multiple colored electrochromic layers, thereby adjusting the color of the entire device to neutral or close to neutral. The color of the device is more in line with people's intuitive perception, which has the effect of alleviating people's visual impact.

[0124] The performance of the ion storage layer provided in this application is further described in detail below by preparing an electrochromic device by combining the ion storage layer and the electrochromic layer.

[0125] The raw materials involved in the specific embodiments of this application are all conventional commercial products. Some of the raw materials in each embodiment are as follows. You can choose to meet the following conditions without affecting the effects of this application. It is worth noting that the following materials are only for illustration.

[0126] Polydimethylsiloxane: number average molecular weight is 2000;

[0127] Sodium tripolyphosphate: 368;

[0128] Polyoxyethylene oxypropylene glycerol: number average molecular weight is 4500;

[0129] Polythiophene: number average molecular weight is 48,000;

[0130] Polypyrrole: number average molecular weight is 30,000;

[0131] Triphenylamine polymer: number average molecular weight is 30,000;

[0132] Polyvinylidene fluoride: number average molecular weight is 150,000;

[0133] Styrene-butadiene rubber: number average molecular weight is 40,000;

[0134] Polysorbate: number average molecular weight is 605;

[0135] Polyethylene oxide (PEO): number average molecular weight is 750;

[0136] Polyvinyl butyral (PVB): number average molecular weight is 80,000;

[0137] TiO2 (particle size 150 nm);

[0138] TiO2 (particle size 80 nm);

[0139] NbO2 (particle size 150nm).

[0140] Example 1

[0141] This embodiment provides an ion storage layer and an electrochromic device. Taking the total mass of the ion storage layer as 100%, the ion storage layer includes the following components in terms of mass percentage:

[0142] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -2, and the b* value is: 2.

[0143] The preparation of an electrochromic device comprises the following steps:

[0144] Preparation of the ion storage layer: The above components are mixed and dispersed in an ethanol solution, then applied to the conductive surface of the first conductive substrate layer by spin coating. After drying, the ion storage layer is obtained. The first conductive substrate layer comprises a first transparent substrate layer and a first transparent conductive layer. The first transparent conductive layer is disposed on one side of the first transparent substrate layer. The ion storage layer is sprayed onto the side of the first transparent conductive layer facing away from the transparent substrate layer by spin coating. After drying, the ion storage layer is obtained. The first transparent substrate layer is a PET film, and the first transparent conductive layer is an ITO film.

[0145] Preparation of the electrochromic layer: An electrochromic material, such as WO3, is applied to the conductive surface of the second conductive substrate layer and dried to form the electrochromic layer. The second conductive substrate layer comprises a second transparent substrate layer and a second transparent conductive layer. The electrochromic layer is disposed on the side of the second transparent conductive layer facing away from the second transparent substrate layer. The second transparent substrate layer is a PET film, and the second transparent conductive layer is ITO.

[0146] Preparation of electrochromic film: The ion storage layer and the electrochromic layer are placed opposite each other, and the electrolyte (PEO, PVB and LiPF6 with a mass ratio of 1:1:0.5) is dripped between the ion storage layer and the electrochromic layer. Then, the ion storage layer and the electrochromic layer are placed opposite each other in a roll-to-roll manner and the electrolyte is sandwiched. The electrolyte is solidified to form an electrochromic film.

[0147] Arrange electrodes: Alternately arrange first and second grooves around the electrochromic film. The first grooves penetrate the first conductive substrate, ion storage layer, electrolyte layer, and electrochromic layer, leaking out of the second transparent conductive layer. The second grooves penetrate the second conductive substrate, ion storage layer, electrolyte layer, and electrochromic layer, leaking out of the first transparent conductive layer. A first bus bar and a second bus bar are arranged on either side of the electrochromic film in the thickness direction. The first bus bar is electrically connected to the first conductive layer, and the second bus bar is electrically connected to the second conductive layer. Then, electrodes are connected to both the first and second bus bars to prepare the electrochromic device.

[0148] Example 2

[0149] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0150] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -2, and the b* value is: 10.

[0151] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0152] Example 3

[0153] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0154] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -3, and the b* value is: 14.

[0155] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0156] Example 4

[0157] This embodiment provides an ion storage layer and an electrochromic device. Taking the total mass of the ion storage layer as 100%, the ion storage layer includes the following components in terms of mass percentage:

[0158] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: 0, and the b* value is: 10.

[0159] In the preparation of the ion storage layer, the above components were substituted for those in Example 1, and in the preparation of the electrochromic layer, the electrochromic layer made of WO3 was replaced with an electrochromic layer made of triphenylamine polymer. The other steps were the same as in Example 1.

[0160] Example 5

[0161] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0162] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -9, and the b* value is: -15.

[0163] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0164] Example 6

[0165] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0166] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -3, and the b* value is: 16.

[0167] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0168] Example 7

[0169] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0170] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is 0, and the b* value is 4.

[0171] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0172] Example 8

[0173] This embodiment provides an ion storage layer and an electrochromic device. The difference between the embodiment 1 and the embodiment 1 is that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0174] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is 2, and the b* value is 20.

[0175] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0176] Example 9

[0177] This embodiment provides an ion storage layer and an electrochromic device. The difference between this embodiment and embodiment 2 is that the butylated hydroxyanisole in embodiment 2 is replaced by phytic acid of the same mass, and the 1,1-diphenylethylene is replaced by phenyl o-hydroxybenzoate of the same mass. Based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0178] After mixing the components except the basic component of the ion storage layer, the a* value defined by the Lab color space is: -1, and the b* value is: 8.

[0179] In the preparation of the ion storage layer, the above components are substituted for the components of the ion storage layer in Example 2, and the other steps are the same as those in Example 2.

[0180] Comparative Example 1

[0181] This comparative example provides an ion storage layer and an electrochromic device, which differ from Example 1 only in that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0182] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 1, and other steps were the same as in Example 1.

[0183] Comparative Example 2

[0184] This comparative example provides an ion storage layer, which differs from Example 4 only in that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components in terms of mass percentage:

[0185] In preparing the ion storage layer, the above components were substituted for the components of the ion storage layer in Example 4, and the other steps were the same as those in Example 4.

[0186] Performance Testing

[0187] The ion storage layers and electrochromic devices provided in Examples 1-9 and Comparative Examples 1-2 were subjected to the following performance tests.

[0188] Lab value: Each of the above-mentioned electrochromic devices was placed at room temperature and charged and discharged respectively to reach its brightest state and darkest state. The brightest state refers to the state with the highest transmittance of the electrochromic device, and the darkest state refers to the state with the lowest transmittance of the electrochromic device. The a* and b* values ​​corresponding to the electrochromic device in the dark state were tested using a colorimeter; the values ​​are recorded in Table 1 below.

[0189] Life test: Each of the above-mentioned electrochromic devices is placed at a high temperature of 85°C. According to the preset charging logic, the electrochromic device is fully charged and fully discharged as one cycle, and the process is performed alternately. Depending on the specific electrochromic material, the preset charging logic is different. The logic used in the embodiment described in this application is: the charging logic is -0.7V discharge, 40 mA cutoff, to achieve full discharge; 0.7V charging, 40 mA cutoff, to achieve full charge. In the cycling process of each electrochromic device, one full charge and discharge cycle is recorded as one circle, and the number of cycles when each electrochromic device shows appearance failure (i.e., a color difference between the local area and the surrounding area) is recorded; this is used to characterize the life of the electrochromic device and is recorded in Table 1 below.

[0190] The test results are summarized in Table 1.

[0191] Table 1

[0192] Analysis of the data in Table 1 shows that, under the premise that the materials of the electrochromic layer and the materials of the basic components of the ion storage layer are the same, compared with the electrochromic device formed by the ion storage layer without adding at least one of the antioxidant, light stabilizer and heat stabilizer, the electrochromic device formed by the ion storage layer made by adding at least one of the antioxidant, light stabilizer and heat stabilizer in the present application has a longer life and more cycles.

[0193] The ion storage layer has high stability and can improve the adhesion with the electrolyte layer and the ITO layer. The electrochromic device formed by the ion storage layer provided in the embodiment of the present application uses an ion storage layer containing a stabilizer, so the life of the electrochromic device is significantly increased compared to the related art. During use, the color change speed is not easy to decline, and the color change range is maintained for a longer time, which has a significant effect of improving the life. In Example 1, the antioxidant is close to a neutral color and the light stabilizer is a neutral color. The electrochromic device obtained shows a color close to the electrochromic layer itself. The ion storage layer has a weak color adjustment function, a life of 35,000 cycles, high stability, and a long time to maintain the color change range.

[0194] In Example 2, the antioxidant and light stabilizer are both yellow in color, and the color of the resulting ion storage layer matches the color of the electrochromic material layer (blue) of the electrochromic device. This allows the color of the electrochromic device to be adjusted during the color change process and at the end of the dark state, so that the a* and b* values ​​approach 0, and the color can be adjusted to be closer to neutral. In addition, the total mass of the three stabilizers added—the antioxidant, light stabilizer, and heat stabilizer—accounts for 10% of the total mass of the ion storage layer, significantly extending the service life of the electrochromic device.

[0195] In Examples 3 and 5, different antioxidants were added, but the amounts of antioxidant added were similar, indicating that the corresponding electrochromic devices had similar service lives. However, due to the different antioxidants added, the corresponding a* and b* values ​​were different, and the color of the corresponding electrochromic devices in the dark state was also different. Therefore, it is proven that adding additives of different colors can not only improve the service life of electrochromic devices, but also play a role in adjusting the color of electrochromic devices when darkened, allowing electrochromic devices to meet more user needs.

[0196] Example 6 adds three stabilizers, including an antioxidant, a light stabilizer, and a heat stabilizer. The sum of their corresponding masses accounts for 20% of the total mass of the ion storage layer. Compared with Comparative Example 1 in which no stabilizer is added, the performance of the electrochromic device is improved to a certain extent, but the improvement is not obvious.

[0197] Example 7 adds three stabilizers, including an antioxidant, a light stabilizer, and a heat stabilizer. The sum of their corresponding masses accounts for less than 1% of the total mass of the ion storage layer. Compared with Comparative Example 1 in which no stabilizer is added, the performance of the electrochromic device is improved to a certain extent, but the improvement is not obvious.

[0198] If the sum of the masses of the antioxidant, light stabilizer and heat stabilizer accounts for too large a proportion of the total mass of the ion storage layer, exceeding 20% ​​(Example 8), the basic components of the corresponding ion storage layer will be reduced, and the life of the corresponding device will be reduced. This proves that the performance of the ion storage layer prepared when the sum of the masses of the antioxidant, light stabilizer and heat stabilizer accounts for the total mass of the ion storage layer within a specific range is better.

[0199] Example 9 changes the materials used for the antioxidant and light stabilizer, but the combined mass of the antioxidant, light stabilizer, and heat stabilizer accounts for 10% of the total mass of the ion storage layer. This significantly increases the lifespan of the electrochromic device. It also adjusts the final color of the entire device, making the color of the electrochromic device closer to neutral at the end of the dark state.

[0200] Analysis of Comparative Example 1 and Example 1 shows that the performance of Comparative Example 1 is inferior to that of Example 1. The addition of a near-neutral antioxidant and a neutral-colored light stabilizer to Example 1 improves the stability of the electrochromic device, thereby extending its service life. However, the Lab value corresponding to the dark-state color change endpoint indicates that the addition of the neutral-colored additive has a weak effect on regulating the final color of the electrochromic device. The electrochromic device still largely assumes the color of the electrochromic layer material. The overall color of the electrochromic device at the dark-state color change endpoint or during the color change process is blue, rather than neutral.

[0201] Analysis of Comparative Example 2 and Example 4 shows that both Comparative Example 2 and Example 4 use organic materials as the electrochromic layer. If antioxidants, light stabilizers, and heat stabilizers are not added, the life of the electrochromic device is reduced, and the b* value of the dark state becomes smaller, deviating from the neutral color. The performance of Comparative Example 1 is not as good as that of Example 4. Example 4 adds components such as yellow antioxidants, which can greatly improve the life of the electrochromic device. In addition, in addition to ensuring the stability of the electrochromic device, the color of the ion storage layer can also be adapted to the color (blue series) of the electrochromic material layer of the electrochromic device. The a* value and b* value of the electrochromic device during the color change process tend to 0, that is, the color of the entire electrochromic device during the color change process is close to neutral, which can better meet the visual needs of the human eye.

[0202] The ion storage layer provided in Example 1 is compatible with inorganic electrochromic materials, and the ion storage layer provided in Example 4 is compatible with organic electrochromic materials. This demonstrates that the ion storage layer provided in this application is suitable not only for electrochromic layers made of organic materials, but also for electrochromic layers made of inorganic materials, greatly expanding the material selection range for electrochromic devices. In summary, after adding at least one of an antioxidant, a light stabilizer, and a heat stabilizer within a reasonable mass percentage range, the device's service life can be increased by at least 50%, and the color of the electrochromic device can be improved.

[0203] It is worth noting that the test results of the Lab values ​​in this application, the above a* values ​​and b* values ​​have an error range of plus or minus 3 due to the error of the test equipment, which is a normal phenomenon.

[0204] It is worth noting that only some embodiments are listed in the embodiments of this application, and the detailed method of this application is mainly described with the blue electrochromic layer. The electrochromic layer of the electrochromic device can also be other colors such as red and black. In order to match different electrochromic layers, antioxidants, heat stabilizers, and light stabilizers of complementary colors can be selected to prepare the ion storage layer, so that the color of the final electrochromic device is close to neutral to meet people's visual needs. In addition, the corresponding additives are also shown in only some embodiments. For other substances, those skilled in the art can reasonably speculate based on the embodiments of this application, and will not be described one by one here.

[0205] The present application uses the above-mentioned embodiments to illustrate the detailed methods of the present application. However, the present application is not limited to the above-mentioned detailed methods, that is, it does not mean that the present application must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvements to the present application, equivalent replacement of various raw materials of the present application product, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Claims

1. An ion storage layer, characterized in that, Based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components by mass percentage: Among them, at least one of the mass percentages of the antioxidant, the light stabilizer, and the heat stabilizer is not 0%; The basic components of the ion storage layer include at least one of an organic material and an inorganic material.

2. The ion storage layer according to claim 1, characterized in that, The sum of the masses of the antioxidant, the light stabilizer, and the heat stabilizer accounts for 0.5%-20% of the total mass of the ion storage layer.

3. The ion storage layer according to claim 1, characterized in that, The range of the a* value defined by the Lab color space for the components other than the basic components of the ion storage layer after mixing is: -50 to 50, and the range of the b* value is: -60 to 60.

4. The ion storage layer according to claim 1, characterized in that, The range of the a* value defined by the Lab color space for the antioxidant is: -15 to 15, and the range of the b* value is: -35 to 35.

5. The ion storage layer according to claim 1, characterized in that, The antioxidant includes at least one of a radical absorber, a metal ion chelator, and a singlet oxygen quencher.

6. The ion storage layer according to claim 5, characterized in that, The ion storage layer further includes at least one of the following features: The radical absorber includes at least one of butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone, ferrous sulfate, and tocopherol; The metal ion chelator includes at least one of ethylenediaminetetraacetic acid, citric acid, polyphosphoric acid, and phytic acid; The singlet oxygen quencher includes at least one of benzidine, diphenylamine, and β-carotene.

7. The ion storage layer according to claim 1, characterized in that, The range of the a* value defined by the Lab color space for the light stabilizer is: -15 to 50, and the range of the b* value is: -30 to 30.

8. The ion storage layer according to claim 1, characterized in that, The ion storage layer further includes at least one of the following features: The light stabilizer includes at least one of a light screening agent, an ultraviolet absorber, and a radical scavenger; The light screening agent includes at least one of titanium dioxide, zinc oxide, and carbon black; The ultraviolet absorber includes at least one of phenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone; The radical scavenger includes at least one of 2,2,6,6-tetramethylpiperidine oxide, dibutylhydroxytoluene, and 1,1-diphenylethylene.

9. The ion storage layer according to claim 1, wherein The range of the a* value defined by the Lab color space for the heat stabilizer is: -15 to 15, and the range of the b* value is: -30 to 30.

10. The ion storage layer according to claim 1, characterized in that, The heat stabilizer includes at least one of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer.

11. The ion storage layer according to claim 1, wherein The other additives include at least one of a leveling agent, an antifoaming agent, and a dispersing agent.

12. The ion storage layer according to claim 1, wherein The basic components of the ion storage layer include at least one of a metal oxide, a dopant of the metal oxide, and an organic polymer.

13. A method for preparing an ion storage layer, characterized in that, The preparation method includes the following steps: Weigh a preset weight fraction of the antioxidant, the light stabilizer, the heat stabilizer, the other additives, and the basic components of the ion storage layer, mix to obtain a mixture, and then coat the mixture on the conductive surface of the conductive base layer to obtain the ion storage layer.

14. An electrochromic film, characterized in that, The electrochromic film includes an ion storage layer, an electrolyte layer, and an electrochromic layer stacked in sequence, and the ion storage layer is the ion storage layer according to any one of claims 1-12.

15. An electrochromic device, characterized in that, The electrochromic device includes a substrate layer and the electrochromic film according to claim 14.

16. A terminal product, characterized in that, The terminal product includes at least one of the ion storage layer according to any one of claims 1-12, the electrochromic film according to claim 14, and the electrochromic device according to claim 15, wherein the terminal product includes any one of a rearview mirror, a curtain wall, a vehicle sunroof, vehicle side windows, a vehicle windshield, a housing of an electronic product, glasses, a vehicle, or a display panel.

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