Ion storage layer and preparation method and application thereof

Abstract

The invention relates to an ion storage layer and a preparation method and application thereof, and the ion storage layer comprises the following components in percentage by mass: less than or equal to 10% of an antioxidant, less than or equal to 10% of a light stabilizer, less than or equal to 10% of a heat stabilizer, less than or equal to 10% of other additives, and the balance of basic components of the ion storage layer, wherein at least one of the mass percent of the antioxidant, the mass percent of the light stabilizer and the mass percent of the heat stabilizer is not 0%; the basic component of the ion storage layer comprises at least one of an organic material and an inorganic material. The ion storage layer provided by the invention is good in stability, and still has good ion storage performance after long-term illumination and repeated circulation; the electrochromic diaphragm prepared from the ion storage layer provided by the invention solves the technical problems of instability and the like of an electrochromic device in the prior art, and has the advantages of stability, good color changing effect and long service life.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromism, and particularly relates to an ion storage layer, a preparation method thereof, and an application thereof. Background Art

[0002] An electrochromic device includes a first conductive base layer and a second conductive base layer which are oppositely arranged, and an electrochromic layer structure disposed between the first conductive base layer and the second conductive base layer; by applying a voltage to the first conductive base layer and the second conductive base layer, the electrochromic layer structure undergoes reversible and stable color changes in response to the change of the voltage at both ends. Therefore, an electrochromic device can be used to prepare an intelligent device with adjustable optical range.

[0003] In the electrochromic devices in the prior art, during multiple cycles or when being in a light environment for a long time, various index parameters thereof will show a large attenuation, especially the performance attenuation of the ion storage layer. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an ion storage layer, a preparation method thereof, and an application thereof. The electrochromic device formed by the ion storage layer has advantages such as good cycling performance and long service life.

[0005] To achieve this purpose, the present invention adopts the following technical solutions:

[0006] In the first aspect, the present invention provides an ion storage layer. Based on 100% of the total mass of the ion storage layer, the ion storage layer comprises the following components in mass percentages:

[0007]

[0008] Among them, 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%;

[0009] The basic components of the ion storage layer include at least one of an organic material and an inorganic material.

[0010] In the present invention, at least one of an antioxidant, a light stabilizer, and a heat stabilizer and other additives are added to the ion storage layer. With at least one of the antioxidant, the light stabilizer, and the heat stabilizer as the stabilizer, the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated insertion and extraction of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, enabling the ion storage layer to ensure the smooth transition of ions and electrons from other layers to the ion storage layer under long-term light exposure and multiple cycles, ensuring the durability of the performance of the ion storage layer, and thus ensuring the color change speed and the adjustable range of transmittance of the electrochromic device. Moreover, the ion storage layer in the present application always maintains a stable adhesive force with other layers and will not peel off from other layers, thereby maintaining good color change performance; thus, the stability and color change performance of the entire electrochromic device are improved. This solves the technical problems in the prior art, such as the instability of the electrochromic device due to the performance decline of the ion storage layer, and has the advantages of stable and good color change effects and long service life.

[0011] Preferably, the mass percentage of the antioxidant is ≤10% and not equal to 0%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0012] Preferably, the mass percentage of the light stabilizer is ≤10% and not equal to 0%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

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

[0014] Preferably, the mass percentage of the other additives is ≤10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0015] Preferably, 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.

[0016] Exemplarily, the sum of the masses of the antioxidant, the light stabilizer, and the heat stabilizer accounts for 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, or 18% of the total mass of the ion storage layer, etc.

[0017] Preferably, the range of the a* value defined by the Lab color space for the mixture of each component except the basic components of the ion storage layer is: -50 to 50; and the range of the b* value is: -60 to 60.

[0018] Exemplarily, the range of the a* value defined by the Lab color space is from -50 to 50, which can be -45, -40, -30, -20, -10, 0, 10, 20, 30, 40, or 45, etc.; the range of the b* value is from -60 to 60, which can be -55, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50, or 55, etc.

[0019] Preferably, the antioxidant has an a* value range of -15 to 15 and a b* value range of -35 to 35 as defined by the Lab color space.

[0020] Exemplarily, for the antioxidant, the a* value range of -15 to 15 defined by the Lab color space can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12, or 14, etc.; 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.

[0021] Preferably, the antioxidant includes at least one of a radical scavenger, a metal ion chelator, and a singlet oxygen quencher. Typical but non-limiting combinations include: a combination of a radical scavenger and a metal ion chelator, a combination of a metal ion chelator and a singlet oxygen quencher, a combination of a radical scavenger, a metal ion chelator, and a singlet oxygen quencher, etc.

[0022] Preferably, the radical scavenger includes at least one of butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol (antioxidant BHT), tert-butylhydroquinone, ferrous sulfate, and tocopherol. Typical but non-limiting combinations of the radical scavenger 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, etc.

[0023] Preferably, the metal ion chelator includes at least one of ethylenediaminetetraacetic acid (EDTA), citric acid, polyphosphoric acid, and phytic acid. Typical but non-limiting combinations of the metal ion chelator 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.

[0024] Preferably, the singlet oxygen quencher includes at least one of benzidine, diphenylamine, and β-carotene. 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, etc.

[0025] Preferably, the a* value range of the light stabilizer defined by the Lab color space is: -15 to 50, and the b* value range is: -30 to 30. Exemplarily, the a* value range of -15 to 50 of the light stabilizer defined by the Lab color space can 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 can be -28, -26, -24, -20, -18, -15, -10, -8, -5, 0, 5, 10, 12, 15, 18, 20, 22, 25, or 28, etc.

[0026] Preferably, the light stabilizer includes at least one of a light screening agent, an ultraviolet absorber, and a radical scavenger.

[0027] Preferably, the light screening agent includes at least one of titanium dioxide, zinc oxide, and carbon black.

[0028] Preferably, the ultraviolet absorber includes at least one of phenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.

[0029] Preferably, the radical scavenger includes at least one of 2,2,6,6-tetramethylpiperidine oxide, dibutylhydroxytoluene, and 1,1-diphenylethylene. Among them, typical but non-limiting combinations of the radical scavenger include: the combination of 2,2,6,6-tetramethylpiperidine oxide and dibutylhydroxytoluene, the combination of dibutylhydroxytoluene and 1,1-diphenylethylene, the combination of 2,2,6,6-tetramethylpiperidine oxide, dibutylhydroxytoluene, and 1,1-diphenylethylene, etc.

[0030] Preferably, the a* value range of the heat stabilizer defined by the Lab color space is: -15 to 15, and the b* value range is: -30 to 30. Among them, -15 to 15 can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12, 14, etc.; -30 to 30 can be -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, etc.

[0031] Preferably, the heat stabilizer includes at least one of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer. Among them, typical but non-limiting combinations of the heat stabilizer include: the combination of a tin stabilizer and a lead stabilizer, the combination of a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer, the combination of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer, etc.

[0032] Preferably, the heat stabilizer includes tribasic sulfate and / or calcium stearate.

[0033] Preferably, the tribasic sulfate includes sodium tribasic sulfate and / or lead tribasic sulfate.

[0034] Preferably, the other additives include at least one of a leveling agent, an antifoaming agent, and a dispersant. Typical but non-limiting combinations include: a combination of a leveling agent and an antifoaming agent, a combination of an antifoaming agent and a dispersant, a leveling agent, a combination of an antifoaming agent and a dispersant, etc.

[0035] Preferably, in the basic components of the ion storage layer, 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.

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

[0037] Preferably, in 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. 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.

[0038] Exemplarily, the nickel oxide includes nickel monoxide (NiO).

[0039] Exemplarily, the molecular formula of the vanadium oxide is VO x , where the value of x satisfies the valence, for example, vanadium monoxide, vanadium sesquioxide, vanadium dioxide, or vanadium pentoxide.

[0040] Exemplarily, the titanium oxide includes titanium dioxide (TiO2) and / or titanium monoxide (TiO).

[0041] Exemplarily, the molecular formula of the niobium oxide is NbO x , where the value of x satisfies the valence, for example, niobium monoxide, niobium dioxide, niobium sesquioxide, or niobium pentoxide.

[0042] Preferably, the dopant of the metal oxide includes tantalum-doped titanium dioxide and / or niobium-doped indium oxide.

[0043] Preferably, the organic polymer includes at least one of triphenylamine polymer, polythiophene and polypyrrole. Typical but non-limiting combinations of the organic polymers include: the combination of triphenylamine polymer and polythiophene, the combination of polythiophene and polypyrrole, the combination of triphenylamine polymer, polythiophene and polypyrrole, etc.

[0044] 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.

[0045] Exemplarily, the mass of the binder accounts for 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5% etc. 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, such as 0.2%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.3%, 2.5% or 2.8% etc.; specifically, the specific types and addition amounts can be selected according to actual needs.

[0046] In a second aspect, the present invention provides a method for preparing an ion storage layer as described in the first aspect. The preparation method includes the following steps:

[0047] Weigh antioxidants, light stabilizers, heat stabilizers, other additives and basic components of the ion storage layer in preset mass percentages, mix them to obtain a mixture, and then coat the mixture on the conductive surface of the conductive base layer to obtain an ion storage layer.

[0048] Preferably, the preset mass percentages are antioxidant ≤10%, light stabilizer ≤10%, heat stabilizer ≤10%, other additives ≤10%, and the basic components of the ion storage layer up to 100%; among them, at least one of the mass percentages of the antioxidant, the light stabilizer and the heat stabilizer is not 0%.

[0049] Preferably, the coating method includes magnetron sputtering or wet coating.

[0050] Preferably, the wet coating includes spin coating.

[0051] In a third aspect, the present invention provides an electrochromic film. 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 as described in the first aspect.

[0052] In the present invention, 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 on the one hand. 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 insertion and extraction of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, enabling the ion storage layer to ensure the smooth transition of ions and electrons from other layers to the ion storage layer under long-term light exposure and multiple cycles, thereby ensuring the color change speed and adjustable transmittance range of the electrochromic device.

[0053] In addition, when forming the electrochromic film, it is also necessary to select a stable additive with a complementary color according to the color of the electrochromic layer material. For example, when the electrochromic material layer is bluish in the dark state, at this time, b* of the electrochromic material layer < 0; an antioxidant in the yellow series with b* > 0, such as butylated hydroxyanisole, a light stabilizer in the yellow series, such as: 2,4,6-tris(2'-n-butoxyphenyl)-1,3,5-triazine, or a heat stabilizer in the yellow series can be added to make the overall color of the electrochromic device closer to neutral; when the electrochromic material layer is reddish, at this time, a* of the electrochromic material layer > 0, an antioxidant in the green series with a* < 0, a light stabilizer in the green series, such as: nickel bis(4-tert-octylphenoxy) sulfide, or a heat stabilizer in the green series can be added to make the overall color of the electrochromic device close to neutral; preferably, the specific added content does not exceed 20%, to avoid the color of the electrochromic device being affected by the additive and showing the color of the additive when in the transparent state, which affects the visual effect of the user.

[0054] The conductive substrate described in the present invention includes a transparent base layer and a transparent conductive layer. The transparent conductive layer is disposed on one side of the base layer, and the ion storage layer is disposed on the side of the transparent conductive layer facing away from the base layer; the transparent base layer includes but is not limited to: glass, plexiglass, and flexible substrates such as polyethylene terephthalate (PET) film, polycarbonate (PC) film, etc.; the conductive layer includes conductive oxides, such as ITO, IZO, etc.

[0055] Fourthly, the present invention provides an electrochromic device, and the electrochromic device includes the electrochromic film described in the third aspect.

[0056] Fifthly, the present invention provides a terminal product, and the terminal product includes at least one of the ion storage layer described in the first aspect, the electrochromic film described in the third aspect, and the electrochromic device described in the fourth aspect. Among them, the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, a housing of an electronic product, glasses, a means of transportation, or a display panel.

[0057] Compared with the prior art, the present invention has the following beneficial effects:

[0058] For the electrochromic device formed by the ion storage layer provided by the present invention, since the ion storage layer includes at least one of an antioxidant, a light stabilizer, and a heat stabilizer, the service life of this electrochromic device is significantly longer than that of the electrochromic device in the prior art. During use, the color change speed is not easily degraded, and the time for maintaining the color change range is longer, having a remarkable effect of improving the service life. Detailed implementation manners

[0059] The technical solution of the present invention will be further described below through specific implementation manners. It should be noted that as long as there is no conflict, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the formed technical solution is within the protection scope of the present invention. Those skilled in the art should understand that the described embodiments are only to help understand the present invention and should not be regarded as specific limitations on the present invention.

[0060] The inventors carefully studied and found that after the electrochromic device undergoes multiple cycles or is in a light environment for a long time, the electrochromic device will exhibit phenomena such as a narrowing of the color change end point range or a slowdown in the color change speed, and other degradation of color change performance. One of the reasons for the degradation of its color change performance is that some components of the ion storage layer (such as adhesives or surfactants, etc.) will age and fail after long-term light exposure 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, due to the failure of some components (such as adhesives or surfactants, etc.) after light exposure, the wettability and adhesion between the ion storage layer and other layers become poor, thereby reducing the jump of ions or electrons from other layers to the ion storage layer, resulting in an increase in the internal resistance of the entire device, and thus leading to performance degradation such as a decrease in the color change speed and a narrowing of the adjustable transmittance range of the entire device; even resulting in a low adhesion between the ion storage layer and other layers and separation from other layers, ultimately causing the entire electrochromic device to lose its color change and dimming functions.

[0061] In view of the above problems, the first aspect of the present application provides an ion storage layer. Based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components in mass percentages:

[0062]

[0063] Among them, 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%;

[0064] The basic components of the ion storage layer include at least one of an organic material and an inorganic material.

[0065] In the embodiment of the present application, at least one of an antioxidant, a light stabilizer, and a heat stabilizer and other additives are added to the ion storage layer. Using at least one of the antioxidant, the light stabilizer, and the heat stabilizer as a stabilizer, the ion storage layer will not be oxidized and lose its activity after long-term exposure to light and heat and repeated insertion and extraction of ions. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, enabling the ion storage layer to ensure the smooth transition of ions and electrons from other layers to the ion storage layer under long-term light exposure and multiple cycles, ensuring the durability of the performance of the ion storage layer, and thus ensuring the color change speed and the adjustable range of transmittance of the electrochromic device. Moreover, the ion storage layer in the present application always maintains a stable adhesion force with other layers and will not peel off from other layers, maintaining good color change performance; thereby improving the stability and color change performance of the entire electrochromic device. This solves the technical problems in the prior art, such as the instability of the electrochromic device due to the performance degradation of the ion storage layer, and has the advantages of stable and good color change effects and long lifespan.

[0066] Exemplarily, the mass percentage of the antioxidant is ≤10% and not equal to 0%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0067] Exemplarily, the mass percentage of the light stabilizer is ≤10% and not equal to 0%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0068] Exemplarily, the mass percentage of the heat stabilizer is ≤10% and not equal to 0%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0069] Exemplarily, the mass percentage of the other additives is ≤10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0070] In the present invention, the mass percentages of the antioxidant, light stabilizer, heat stabilizer and other additives are each independently preferably ≤10%. The reason is that when the mass percentages of the antioxidant, light stabilizer, heat stabilizer and other additives are all controlled within 10%, it can avoid the weakening of the ion storage ability of the ion storage layer caused by excessive content of the basic components of the non-ionic storage layer. In addition, the antioxidant, light stabilizer and heat stabilizer are all stable additives for the ion storage layer. Different stable additives can be selected according to different devices used in different environments. For example, in an indoor environment with weak light, an antioxidant or heat stabilizer can be selected. When applied to electrochromic devices such as curtain walls and automotive sunroofs that are exposed to the outdoor environment for a long time, a light stabilizer can be selected as the main stable additive. Of course, a mixture of antioxidant, light stabilizer, heat stabilizer, etc. can also be used as a stable additive.

[0071] Exemplarily, 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, such as 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16% or 18%, etc.

[0072] In the present invention, the total mass of the antioxidant, light stabilizer and heat stabilizer is controlled 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 percentage of the basic components of the ion storage layer will be relatively reduced, thus affecting the ion storage ability 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, which can not only ensure the ion storage ability, but also improve the stability of the ion storage layer, and then improve the service life of the electrochromic device. Specifically, the specific component contents of the antioxidant, light stabilizer and heat stabilizer, etc. are determined according to the specific components of the ion storage layer. Preferably, the total mass of the oxidant, light stabilizer and heat stabilizer accounts for 0.5%-10% of the total mass of the ion storage layer.

[0073] Exemplarily, the range of the a* value defined by the Lab color space for the mixture of each component other than the basic components of the ion storage layer is: -50 to 50; and the range of the b* value is: -60 to 60, where -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.

[0074] In the present invention, in the three-layer structure of the electrochromic film of the prior art, the ion storage layer is usually colorless, and the electrolyte layer is also colorless. However, the electrochromic layer has a color, usually bluish or greenish, resulting in the color change end point of the electrochromic film, especially the color change end point in the dark state, being blue or green. By adding an ion storage layer capable of complementary coloring with the color of the electrochromic layer, the electrochromic film maintains color neutrality or approaches neutrality during the color change process or at the color change end point in the dark state, improving the appearance consistency.

[0075] In the present invention, "neutral" color refers to: in the Lab value, the a* value and the b* value are equal to 0, and the color effect is neutral, that is, colorless (neutral color). When the a* value and the b* value in the Lab value tend to 0, the color effect approaches neutrality. A color effect of neutral or approaching neutrality is more friendly to the visual impact of people.

[0076] It should be noted that the L*, a*, and b* values in the Lab color space represent the brightness, red-green chromaticity, and yellow-blue chromaticity of the color, respectively. The Lab value includes the a* value and the b* value. When the L* value is larger, it indicates that the brightness of the color is higher. When a*>0, it indicates that the color belongs to the red color system, and the larger the a* value, the more reddish the color; when a*<0, it indicates that the color belongs to the green color system, and the smaller the a* value, the more greenish the color. When b*>0, it indicates that the color belongs to the yellow color system, and the larger the b* value, the more yellowish the color; when b*<0, it indicates that the color belongs to the blue color system, and the smaller the b* value, the more bluish the color. Color parameters: The L* value (Lightness, brightness) ranges from 0 to 100, 0 represents black, and 100 represents white; the a* value (Redness, red chromaticity) represents the color between red and green, 100 is red, and -80 is green; the b* value (Yellowness, yellow chromaticity) represents the color between yellow and blue, 100 is yellow, and -80 is blue. The closer the a* value and the b* value are to 0, the closer the color is to neutrality, and the more comfortable it is for the human eye. The L* value changes with the transmittance affected by the voltage of the electrochromic device; for example, the electrochromic device changes its own transmittance under the influence of the voltage at both ends. When the electrochromic device changes color in response to the voltage to a transmittance of 100%, the L* value is 100 at this time. If the transmittance of the electrochromic device is 0%, the corresponding L* value is 0. The adjustable transmittance range of the electrochromic device is affected by the material of the electrochromic layer.

[0077] In the embodiments of the present application, the electrochromic device changes its transmittance by changing its own color by applying a voltage to the two conductive layers of the device. The electrochromic device usually switches between the colored state, the intermediate state, and the transparent state. The colored states include green, black, blue, red, etc. In the prior art, when the electrochromic device switches between any two states of the colored state, the intermediate state, and the transparent state or reaches the color change end point, the color of the electrochromic device is bluish at the color change end point or appears greenish during the color change process, causing visual discomfort to the user. Further, in the prior art, the reason for the visual discomfort caused by the color during the color change process in the electrochromic device is that the electrochromic material layer usually has a color, 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 nearly neutral color. Therefore, in the present invention, a trace amount of a 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 color change end point. Without changing the material properties of the electrochromic material layer and adding a stabilizing additive with a color, the stability of the device can be improved, and at the same time, the entire color change process of the electrochromic device is neutral or nearly neutral, closer to the human visual effect and improving the comfort level, without causing visual impact to the user and reducing the user experience.

[0078] Exemplarily, the a* value of the antioxidant defined by the Lab color space has a range of: -15 to 15; the b* value has a range of: -35 to 35, where -15 to 15 can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12, or 14, etc.; -35 to 35 can be -30, -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, or 30, etc.

[0079] In the present invention, the preferred range of the a* value defined by the Lab color space of the antioxidant is: -15 to 15; the preferred range of the b* value is: -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 close to the neutral color, so that the ion storage layer has a color adapted to the electrochromic layer, and further adapted to the electrochromic material layer of the electrochromic device. When the electrochromic device is in the process of color change or at the end point of color change, its color is closer to the neutral color, which can better meet the visual needs of users and improve the user experience. In addition, the addition of the antioxidant 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 antioxidant and selecting an antioxidant with a color close to neutral, the initial color of the entire device is not affected even when a small amount of antioxidant is added, ensuring the appearance of the electrochromic device in the faded state and avoiding the electrochromic device in the faded state from presenting a non-neutral color, further meeting the visual needs of users.

[0080] Exemplarily, the antioxidant includes at least one of a radical absorber, a metal ion chelator, and a singlet oxygen quencher. Typical but non-limiting combinations include: a combination of a radical absorber and a metal ion chelator, a combination of a metal ion chelator and a singlet oxygen quencher, a combination of a radical absorber, a metal ion chelator, and a singlet oxygen quencher, etc.

[0081] Exemplarily, the radical absorber includes at least one of butylated hydroxyanisole, antioxidant BHT, tert-butylhydroquinone, ferrous sulfate, and tocopherol. 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, etc.

[0082] Exemplarily, the metal ion chelator includes at least one of ethylenediaminetetraacetic acid, citric acid, polyphosphoric acid, and phytic acid. Typical 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, etc.

[0083] Exemplarily, the singlet oxygen quencher includes at least one of benzidine, diphenylamine, and β-carotene. 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, etc.

[0084] Exemplarily, the a* value range of the light stabilizer defined by the Lab color space is: -15 to 50, and the b* value range is: -30 to 30. Among them, -15 to 50 can be -13, -12, -10, -8, -6, -4, -2, 0, 10, 20, 25, 30, 35, 40 or 45, etc.; -30 to 30 can be -28, -26, -24, -20, -18, -15, -10, -8, -5, 0, 5, 10, 12, 15, 18, 20, 22, 25 or 28, etc.

[0085] In the present invention, 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 a wider Lab value range can meet the color adjustment of a wider range of colors, enabling the ion storage layer to adapt to more different color electrochromic layers. In addition, when the electrochromic device is applied in a relatively harsh environment, such as long-term exposure to sunlight, etc., it is easy to accelerate the aging speed, causing the device itself to turn yellow. The wider color range of the ion storage layer can meet the complementary color of the device aging discoloration, making the color of the electrochromic device approach neutral throughout its entire life cycle, reducing the possibility of the electrochromic device being eliminated due to color affecting its appearance, and further improving the service life of the electrochromic device. Further, by selecting the a* and b* values of the light stabilizer within a certain range, and the a* and b* values of the light stabilizer within this range can also block part of the blue-violet light, which helps to improve the light resistance performance of the electrochromic device, while reducing the influence of the electrochromic device being affected by blue-violet light and reducing its stability, thereby improving the stability of the electrochromic device.

[0086] Exemplarily, the light stabilizer includes at least one of a light shielding agent, an ultraviolet absorber, and a radical scavenger.

[0087] Exemplarily, the light shielding agent includes at least one of titanium dioxide, zinc oxide, and carbon black.

[0088] Exemplarily, the ultraviolet absorber includes at least one of phenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.

[0089] Exemplarily, the radical scavenger includes at least one of 2,2,6,6-tetramethylpiperidine oxide, dibutylhydroxytoluene, and 1,1-diphenylethylene. Among them, typical but non-limiting combinations include: the combination of 2,2,6,6-tetramethylpiperidine oxide and dibutylhydroxytoluene, the combination of dibutylhydroxytoluene and 1,1-diphenylethylene, the combination of 2,2,6,6-tetramethylpiperidine oxide, dibutylhydroxytoluene and / or 1,1-diphenylethylene, etc.

[0090] Exemplarily, the a* value range of the heat stabilizer defined by the Lab color space is: -15 to 15, and the b* value range is: -30 to 30. Among them, -15 to 15 can be -12, -10, -8, -6, -4, -2, 0, 2, 4, 6, 8, 10, 12, 14, etc.; -30 to 30 can be -25, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, etc.

[0091] In the present invention, the a* value range of the heat 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 heat stabilizer with a certain color is selected, and the a* value and b* value of the heat stabilizer are close to the neutral color, so that the ion storage layer has a color adapted to the electrochromic layer, and further adapted to the electrochromic material layer of the electrochromic device, so that when the electrochromic device is in the process of color change or at the end point of color change, especially at the end point of the dark state, its color is closer to the neutral color, which can better meet the visual needs of users and improve the user experience. In addition, the addition of the heat 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 added heat stabilizer and selecting a heat stabilizer with a color close to neutral, the initial color of the entire device is not affected when adding a small amount of heat stabilizer, ensuring the appearance of the electrochromic device in the faded state and avoiding the electrochromic device in the faded state presenting a non-neutral color, further meeting the visual needs of users.

[0092] Exemplarily, the heat stabilizer includes at least one of a tin stabilizer, a lead stabilizer, a mixed metal stabilizer, and a Group IIA metal stabilizer. Among them, 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, etc.

[0093] Exemplarily, the heat stabilizer includes tribasic sulfate and / or calcium stearate.

[0094] Exemplarily, the tribasic sulfate includes tribasic sodium sulfate and / or tribasic lead sulfate.

[0095] Exemplarily, the other additives include at least one of a leveling agent, an antifoaming agent, and a dispersant. Among them, typical but non-limiting combinations include: a combination of a leveling agent and an antifoaming agent, a combination of an antifoaming agent and a dispersant, a combination of a leveling agent, an antifoaming agent, and a dispersant, etc.

[0096] Exemplarily, the leveling agent includes polydimethylsiloxane and / or dioctyl phthalate; the defoaming agent includes sodium tripolyphosphate; the dispersant includes tetraethyl orthosilicate and / or polyoxyethylene oxypropylene glycerol. The other additives include any one or a combination of at least two of polydimethylsiloxane, dioctyl phthalate, polyoxyethylene oxypropylene glycerol, sodium tripolyphosphate or tetraethyl orthosilicate. Typical but non-limiting combinations include: the combination of polydimethylsiloxane and sodium tripolyphosphate, the combination of sodium tripolyphosphate and tetraethyl orthosilicate, the combination of polydimethylsiloxane, sodium tripolyphosphate and tetraethyl orthosilicate.

[0097] In a preferred embodiment of the present invention, the leveling agent is added to adjust the leveling property of the ion storage layer, so that the ion storage layer has a high leveling effect when coated on the conductive substrate, making the thickness of the ion storage layer more uniform. In addition, a defoaming agent is added to reduce the generation of foam during the stirring of the ion storage layer. In the preferred embodiment of the present invention, a dispersant is added to make the components of the ion storage layer more uniformly dispersed, so that the ion storage capacity at each point of the ion storage layer is uniform, and the stability is also uniform, thereby improving the stability of the electrochromic device.

[0098] Exemplarily, in the basic components of the ion storage layer, the basic components of the ion storage layer include at least one of metal oxides, dopants of metal oxides, and organic polymers.

[0099] In the embodiments of the present application, the basic components of the ion storage layer are preferably at least one of metal oxides, dopants of metal oxides, and organic polymers. The reason is that they have a high ion storage capacity. Whether it is an organic system or an inorganic system, the improvement of the ion storage layer provided by the present application can ensure the original ion storage capacity of the ion storage layer, while ensuring the stability of the ion storage layer, improving the stability of the ion storage layer and further improving the service life of the electrochromic device.

[0100] Exemplarily, the basic components of the ion storage layer include at least one of metal oxides and dopants of metal oxides. The metal oxide or the metal oxide has a high ion storage capacity, and the number of its cycling times can reach tens of thousands of cycles, further improving the service life of the electrochromic device. Typical but non-limiting combinations include: the combination of metal oxides and dopants of metal oxides, the combination of dopants of metal oxides and organic polymers, the combination of metal oxides, dopants of metal oxides and organic polymers, etc.

[0101] Exemplarily, in 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. 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.

[0102] In the embodiments 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 production conditions, enabling the ion storage layer to be prepared at low temperatures without the need for a high-temperature environment, thereby reducing the loss of activity of antioxidants, light stabilizers, heat stabilizers, etc. caused by high-temperature preparation, and thus improving the service life of the ion storage layer.

[0103] Exemplarily, the nickel oxide includes nickel monoxide.

[0104] Exemplarily, the molecular formula of the vanadium oxide is VO x , where the value of x satisfies the valence. For example, vanadium monoxide, vanadium trioxide, vanadium dioxide, or vanadium pentoxide.

[0105] Exemplarily, the titanium oxide includes titanium dioxide and / or titanium oxide.

[0106] Exemplarily, the molecular formula of the niobium oxide is NbO x , where the value of x satisfies the valence. For example, niobium monoxide, niobium dioxide, niobium sesquioxide, or niobium pentoxide.

[0107] Exemplarily, the dopant of the metal oxide includes tantalum-doped titanium dioxide and / or niobium-doped indium oxide.

[0108] Exemplarily, the organic polymer includes at least one of triphenylamine polymer, polythiophene, and polypyrrole. 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, etc.

[0109] Exemplarily, the basic components of the ion storage layer further include an adhesive and a surfactant. The mass of the adhesive accounts for ≤5% of the total mass of the ion storage layer, such as 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, such as 0.2%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, or 2.8%, etc.; specifically, the specific types and addition amounts can be selected according to actual needs.

[0110] In the embodiments of the present application, by adding an adhesive and a surfactant, the adhesion strength between the ion storage layer and other layers is improved. At the same time, by adjusting the Lab values of the selected antioxidants, light stabilizers, heat stabilizers, etc., the influence of the addition of the adhesive and the surfactant on the color of the device is improved, ensuring that the electrochromic device can be more suitable for the comfort level of the human naked eye after adding the adhesive and the surfactant, and improving the user experience. The ion storage layer can form an ion storage layer with excellent comprehensive performance on the basis of adding an adhesive and a surfactant, etc.

[0111] In a second aspect, the present invention provides a method for preparing an ion storage layer as described in the first aspect, and the preparation method includes the following steps:

[0112] Weigh a preset mass percentage of antioxidants, light stabilizers, heat stabilizers, 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 substrate layer to obtain an ion storage layer.

[0113] Preferably, the mass percentage is antioxidant ≤ 10%, light stabilizer ≤ 10%, heat stabilizer ≤ 10%, other additives ≤ 10%, and the basic components of the ion storage layer up to 100%; wherein, at least one of the mass percentages of the antioxidant, the light stabilizer, and the heat stabilizer is not 0%.

[0114] Preferably, the coating method includes magnetron sputtering or wet coating.

[0115] Preferably, the wet coating includes spin coating.

[0116] In a third aspect, the present invention provides an electrochromic film, and 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 as described in the first aspect.

[0117] In the present invention, 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 on the one hand. 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 light exposure, heating, and repeated ion insertion and extraction. While ensuring the ion storage function of the ion storage layer itself, the stability of the ion storage layer is improved, enabling the ion storage layer to ensure the smooth transition of ions and electrons from other layers to the ion storage layer under long-term light exposure and multiple cycles, thereby ensuring the color change speed and the adjustable range of transmittance of the electrochromic device.

[0118] In addition, when forming the electrochromic film, it is also necessary to select a stable additive with a complementary color according to the color of the electrochromic layer material. For example, when the electrochromic material layer is bluish in the dark state, at this time, b* of the electrochromic material layer < 0; an antioxidant in the yellow series with b* > 0, such as butylated hydroxyanisole, a light stabilizer in the yellow series, such as 2,4,6-tris(2'-n-butoxyphenyl)-1,3,5-triazine, or a heat stabilizer in the yellow series can be added to make the overall color of the device closer to neutral; when the electrochromic material layer is reddish, at this time, a* of the electrochromic material layer > 0, an antioxidant in the green series with a* < 0, a light stabilizer in the green series, such as nickel bis(4-tert-octylphenoxy) sulfide, or a heat stabilizer in the green series can be added to make the overall color of the device close to neutral; preferably, the specific added content does not exceed 20%, to avoid the color of the device being affected by the additive and presenting the color of the additive, which affects the visual effect of the user, when in the transparent state.

[0119] The conductive substrate described in the embodiments of the present application includes a transparent base layer and a transparent conductive layer. The transparent conductive layer is disposed on one side of the base layer, and the ion storage layer is disposed on the side of the transparent conductive layer facing away from the base layer; the transparent base layer includes, but is not limited to: glass, plexiglass, and flexible substrates such as PET film, PC film, etc.; the conductive layer includes conductive oxides, such as ITO, IZO, etc.

[0120] Fourthly, the present invention provides an electrochromic device, and the electrochromic device includes the electrochromic film described in the third aspect.

[0121] Fifthly, the present invention provides a terminal product, and the terminal product includes at least one of the ion storage layer described in the first aspect, the electrochromic film described in the third aspect, and the electrochromic device described in the fourth aspect. Among them, the terminal product includes any one of a rearview mirror, a curtain wall, a car sunroof, a car side window, a car windshield, a housing of an electronic product, glasses, a means of transportation, or a display panel.

[0122] The basic component of the ion storage layer described in the present invention can be an organic material or an inorganic material, and the matching of materials is more extensive. The ion storage layer cooperates with an organic or inorganic electrochromic material to form an electrochromic layer, and the further formed electrochromic device has a long service life. Preferably, by adding antioxidants, heat stabilizers, light stabilizers, etc. with colors, the ion storage layer can be adapted to a variety of electrochromic layers with colors, and further adjust the color of the entire device to neutral or approaching neutral, and the color of the device is more in line with people's intuitive feelings, achieving the effect of alleviating the visual impact on people.

[0123] Hereinafter, the ion storage layer and the electrochromic layer are combined to prepare an electrochromic device to further detail the performance of the ion storage layer provided by the present application.

[0124] The raw materials involved in the specific implementation manners in this application are all conventional commercially available products. The following are some of the raw materials in each implementation manner. You can choose to meet the following conditions, which will not affect the effects of the present invention. It should be noted that the following materials are only for illustration purposes.

[0125] Polydimethylsiloxane: number-average molecular weight is 2000;

[0126] Sodium tripolyphosphate: 368;

[0127] Polyoxyethylene oxypropylene glycerol: number-average molecular weight is 4500;

[0128] Polythiophene: number-average molecular weight is 48000;

[0129] Polypyrrole: number-average molecular weight is 30000;

[0130] Triphenylamine polymer: number-average molecular weight is 30000;

[0131] Polyvinylidene fluoride: number-average molecular weight is 150000;

[0132] Styrene-butadiene rubber: number-average molecular weight is 40000;

[0133] Polysorbate: number-average molecular weight is 605;

[0134] Polyethylene oxide (PEO): number-average molecular weight is 750;

[0135] Polyvinyl butyral (PVB): number-average molecular weight is 80000;

[0136] TiO2 (particle size is 150 nm);

[0137] TiO2 (particle size is 80 nm);

[0138] NbO2 (particle size is 150 nm).

[0139] Example 1

[0140] This example provides an ion storage layer and an electrochromic device. Based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0141]

[0142] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: -2 and 2 respectively.

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

[0144] Preparation of the ion storage layer: Mix and disperse the above-mentioned components in an ethanol solution, and then place it on the conductive surface of the first conductive substrate layer by spin coating. After drying, the ion storage layer is obtained. The above-mentioned first conductive substrate layer includes 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. Among them, the first transparent substrate layer is a PET film; the first transparent conductive layer is ITO.

[0145] Preparation of the electrochromic layer: Coat an electrochromic material such as WO3 on the conductive surface of the second conductive substrate layer. After drying, the electrochromic layer is obtained. Among them, the second conductive substrate layer includes 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 the electrochromic film: Oppose the ion storage layer and the electrochromic layer, and dropwise coat an electrolyte (PEO, PVB, and LiPF6 with a mass ratio of 1:1:0.5) between the ion storage layer and the electrochromic layer. Then, in a roll-to-roll manner, make the ion storage layer and the electrochromic layer oppose each other and sandwich the electrolyte, and cure the electrolyte to form an electrochromic film.

[0147] Arrangement of electrodes: Alternately arrange a first groove and a second groove around the electrochromic film. The first groove penetrates through the first conductive substrate, the ion storage layer, the electrolyte layer, and the electrochromic layer to expose the second transparent conductive layer; the second groove penetrates through the second conductive substrate, the ion storage layer, the electrolyte layer, and the electrochromic layer to expose the first transparent conductive layer. A first bus bar and a second bus bar are respectively arranged on both sides 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 bus bar and the second bus bar to prepare an electrochromic device.

[0148] Example 2

[0149] This example provides an ion storage layer and an electrochromic device, the difference from Example 1 being that, based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components in mass percentages:

[0150]

[0151] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: -2 and 10, respectively.

[0152] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 1 with the above components, and the other steps are the same as those in Example 1.

[0153] Example 3

[0154] This example provides an ion storage layer and an electrochromic device. The difference from Example 1 is only that, based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0155]

[0156] The a* value defined by the Lab color space after mixing the components other than the basic components of the ion storage layer is: -3, and the b* value is: 14.

[0157] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 1 with the above components, and the other steps are the same as those in Example 1.

[0158] Example 4

[0159] This example provides an ion storage layer and an electrochromic device. Based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0160]

[0161] The a* value defined by the Lab color space after mixing the components other than the basic components of the ion storage layer is: 0, and the b* value is: 10.

[0162] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 1 with the above components, and replace the electrochromic layer made of WO3 with an electrochromic layer made of triphenylamine polymer in the preparation of the electrochromic layer. The other steps are the same as those in Example 1.

[0163] Example 5

[0164] This example provides an ion storage layer and an electrochromic device. The difference from Example 1 is only that, based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0165]

[0166] The a* value defined by the Lab color space after mixing the components other than the basic components of the ion storage layer is: -9, and the b* value is: -15.

[0167] In the preparation of the ion storage layer, the above components are used to replace the components of the ion storage layer in Example 1, and the other steps are the same as those in Example 1.

[0168] Example 6

[0169] This example provides an ion storage layer and an electrochromic device, the difference from Example 1 being that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components by mass percentage:

[0170]

[0171] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: -3 for a* and 16 for b*.

[0172] In the preparation of the ion storage layer, the above components are used to replace the components of the ion storage layer in Example 1, and the other steps are the same as those in Example 1.

[0173] Example 7

[0174] This example provides an ion storage layer and an electrochromic device, the difference from Example 1 being that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components by mass percentage:

[0175]

[0176] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: 0 for a* and 4 for b*.

[0177] In the preparation of the ion storage layer, the above components are used to replace the components of the ion storage layer in Example 1, and the other steps are the same as those in Example 1.

[0178] Example 8

[0179] This example provides an ion storage layer and an electrochromic device, the difference from Example 1 being that, based on the total mass of the ion storage layer being 100%, the ion storage layer comprises the following components by mass percentage:

[0180]

[0181]

[0182] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: 2 for a* and 20 for b*.

[0183] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 1 with the above components, and the other steps are the same as those in Example 1.

[0184] Example 9

[0185] This example provides an ion storage layer and an electrochromic device, which are different from Example 2 in that butylated hydroxyanisole in Example 2 is replaced with the same mass of phytic acid, and 1,1-diphenylethylene is replaced with the same mass of phenyl o-hydroxybenzoate. Based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0186]

[0187] The a* value defined by the Lab color space and the b* value after mixing the components other than the basic components of the ion storage layer are: -1 and 8, respectively.

[0188] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 2 with the above components, and the other steps are the same as those in Example 2.

[0189] Comparative Example 1

[0190] This comparative example provides an ion storage layer and an electrochromic device, which are different from Example 1 only in that based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0191]

[0192] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 1 with the above components, and the other steps are the same as those in Example 1.

[0193] Comparative Example 2

[0194] This comparative example provides an ion storage layer, which is different from Example 4 only in that based on the total mass of the ion storage layer being 100%, the ion storage layer includes the following components by mass percentage:

[0195]

[0196] In the preparation of the ion storage layer, replace the components of the ion storage layer in Example 4 with the above components, and the other steps are the same as those in Example 4.

[0197] Performance Test

[0198] Perform the following performance tests on the ion storage layers and electrochromic devices provided in Examples 1-9 and Comparative Examples 1-2.

[0199] (1) Lab values: Place the above-mentioned electrochromic devices at room temperature, charge and discharge the electrochromic devices respectively to make them reach the brightest state and the 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. Use a color difference meter to measure the corresponding a* and b* values of the electrochromic device in the dark state; record them in Table 1 below.

[0200] (2) Life test: Place the above-mentioned electrochromic devices at 85 °C respectively. According to the preset charging logic, make the electrochromic device fully charge - fully discharge as one cycle and execute alternately. According to the different specific electrochromic materials, the preset charging logics are different. The logic adopted in the embodiments of the present application is: the charging logic is to discharge at -0.7V and cut off at 40 mA to reach full discharge; charge at 0.7V and cut off at 40 mA to reach full charge. During the cycle of each electrochromic device, record one full charge and full discharge cycle as 1 turn, and record the number of cycles when the appearance of each electrochromic device fails (that is, there is a color difference between the local area and the surrounding area); use this to characterize the life of the electrochromic device and record it in Table 1 below.

[0201] The test results are summarized in Table 1.

[0202] Table 1

[0203] b*-dark state a*-dark state Life / cycle Example 1 -28 9 35000 Example 2 -7 6 15000 Example 3 -3 4 25000 Example 4 -6 10 5000 Example 5 -46 -5 25000 Example 6 -2 4 12000 Example 7 -6 10 11000 Example 8 2 11 9000 Example 9 -8 9 18000 Comparative Example 1 -35 9 10000 Comparative Example 2 -22 6 2000

[0204] Analyzing the data in Table 1, it can be seen that on the premise that the materials of the electrochromic layer and the basic components of the ion storage layer are the same, the electrochromic device formed by the ion storage layer prepared by adding at least one of an antioxidant, a light stabilizer and a heat stabilizer in the present invention has a longer life and more cycles compared with the electrochromic device formed by the ion storage layer without adding at least one of an antioxidant, a light stabilizer and a heat stabilizer.

[0205] The ion storage layer has high stability and can improve the adhesion to the electrolyte layer and the ITO layer. The electrochromic device formed by the ion storage layer provided by the embodiments of the present application has a significantly increased life compared with the prior art due to the use of the ion storage layer containing a stabilizer. During use, the color change speed is not easy to decline, and the time to maintain the color change range is longer, having a significant effect of improving the life. In Example 1, the antioxidant is close to neutral color and the light stabilizer is neutral color. The prepared electrochromic device shows a color close to that of the electrochromic layer itself. The ion storage layer has a weak color mixing function, a life of 35,000 cycles, high stability, and a long time to maintain the color change range.

[0206] In Example 2, the antioxidants and light stabilizers are both yellow in color. The color of the prepared ion storage layer can match the color (blue series) of the electrochromic material layer of the electrochromic device, thereby adjusting the color state of the electrochromic device during the color change process and at the end point of the dark state color change, making the a* value and b* value tend to 0, and the color can be adjusted to be more neutral. In addition, three stabilizers are added. The total mass of the three stabilizers, namely antioxidants, light stabilizers, and heat stabilizers, accounts for 10% of the total mass of the ion storage layer, which can greatly improve the service life of the electrochromic device.

[0207] In Example 3 and Example 5, different antioxidants are added, but the addition amounts of the antioxidants are close, and the service lives of the corresponding electrochromic devices are close. However, due to the different antioxidants added, their corresponding a* values and b* values are different, and the colors of the corresponding electrochromic devices are also different in the dark state. Therefore, it is proved that adding additives of different colors can not only improve the service life of the electrochromic device, but also play a role in adjusting the color of the electrochromic device when it darkens, so that the electrochromic device can meet the needs of more users.

[0208] In Example 6, three stabilizers are added, including antioxidants, light stabilizers, and heat stabilizers. The sum of their corresponding masses accounts for 20% of the total mass of the ion storage layer. Compared with Comparative Example 1 without added stabilizers, the performance of the electrochromic device has a certain improvement, but the improvement is not obvious.

[0209] In Example 7, three stabilizers are added, including antioxidants, light stabilizers, and heat stabilizers. 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 without added stabilizers, the performance of the electrochromic device has a certain improvement, but the improvement is not obvious.

[0210] If the sum of the masses of the antioxidant, light stabilizer, and heat stabilizer is too large and exceeds 20% (Example 8), the basic components of the corresponding ion storage layer decrease, and the life of the corresponding device decreases, which 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.

[0211] In Example 9, the materials of the antioxidant and light stabilizer are changed, but the sum of the masses of the antioxidant, light stabilizer, and heat stabilizer accounts for 10% of the total mass of the ion storage layer, which can greatly improve the service life of the electrochromic device. And it can also adjust the final color of the whole device, making the color of the electrochromic device at the end point of the dark state color change closer to neutral.

[0212] Analysis of Comparative Example 1 and Example 1 shows that the performance of Comparative Example 1 is inferior to that of Example 1. In Example 1, the addition of an antioxidant close to neutral color and a neutral color light stabilizer can improve the stability of the electrochromic device, thereby increasing the service life of the electrochromic device. However, according to the Lab value corresponding to the dark state color change end point, it can be seen that the addition of neutral color additives has a weak effect on adjusting the final color of the electrochromic device. The electrochromic device still largely shows the color of the electrochromic layer material. The dark state color change end point or the overall color during the color change process of the electrochromic device is blue-based and does not have a neutral color.

[0213] 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 service life of the electrochromic device is reduced, and the b* value in the dark state becomes smaller, deviating from the neutral color. The performance of Comparative Example 1 is inferior to that of Example 4. The addition of components such as yellow-based antioxidants in Example 4 can greatly increase the service life of the electrochromic device. In addition, in addition to ensuring the stability of the electrochromic device, it can also make the color of the ion storage layer match the color (blue-based) of the electrochromic material layer of the electrochromic device. The a* value and b* value of the electrochromic device tend to 0 during the color change process, that is, the color of the entire electrochromic device approaches neutral during the color change process, which can better meet the visual needs of the human eye.

[0214] The ion storage layer provided in Example 1 is matched with the inorganic electrochromic material, and the ion storage layer provided in Example 4 is adapted to the organic electrochromic material, proving that the ion storage layer provided by the present invention is not only applicable to the organic electrochromic layer, but also applicable to the inorganic electrochromic layer, greatly expanding the material selection range of the electrochromic device. In summary, after adding at least one of antioxidants, light stabilizers, and heat stabilizers within a reasonable mass percentage range, the service life of the device can be increased by at least 50%, and the color of the electrochromic device can be improved.

[0215] It should be noted that for the test results of the Lab value in this application, the above a* value and b* value have an error range of ±3 due to the test equipment error, which is a normal phenomenon.

[0216] It should be noted that only some embodiments are listed in the embodiments of the present application. Taking the electrochromic layer of the blue color system as the main example to illustrate the detailed method of the present invention, the electrochromic layer of the electrochromic device can also be other colors such as the red color system and the black color system. To match different electrochromic layers, antioxidants, heat stabilizers, and light stabilizers of their complementary color systems can be selected to formulate the ion storage layer, so that the color of the final electrochromic device approaches neutrality to meet the visual needs of people. In addition, only some embodiments of the corresponding additives are shown. For other substances, those skilled in the art can reasonably infer according to the embodiments of the present application, and will not be elaborated here one by one.

[0217] The present invention illustrates the detailed method of the present invention through the above embodiments, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

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 percentage of the antioxidant, the mass percentage of the light stabilizer, and the mass percentage of 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, wherein 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, wherein 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, wherein 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, wherein 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, wherein 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 shielding agent, an ultraviolet absorber, and a radical scavenger; The light shielding 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, characterized in that, 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, characterized in that, 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 onto 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 that are sequentially stacked, and the ion storage layer is the ion storage layer described in any one of claims 1-12.

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

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

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