KR102429311B1 - Electrolyte composition comprising metal organic compound and antioxidant, and electrochromic device comprising the same - Google Patents

Abstract

The present application relates to a method of manufacturing an electrochromic device for a smart window with improved durability through the introduction of an antioxidant, and more specifically, the ratio of the metallocene-based material to the electrolyte layer to improve the durability and reaction rate of the electrochromic device. The present invention relates to improving durability without deterioration of optical properties of an electrochromic device by introducing an antioxidant in order to prevent reverse oxidation and deterioration of durability thereof.

Description

Electrolyte composition comprising metal organic compound and antioxidant, and electrochromic device comprising same

The present application relates to an electrolyte composition including a metal organic compound and an antioxidant, and an electrochromic device including the same. More specifically, in order to improve the durability and reaction rate of the electrochromic element, an antioxidant for preventing the irreversible oxidation of the metal-organic compound injected into the electrolyte layer is introduced to improve the durability without deterioration of the optical properties of the electrochromic element it's about doing

Electrochromism refers to a phenomenon in which the optical properties of an electrochromic material are changed by an electrochemical oxidation or reduction reaction, and a device using this phenomenon is called an electrochromic device. In general, an electrochromic device includes an electrochromic layer, an electrolyte layer, and an ion storage layer between two opposing electrodes, and each of the electrochromic layer and the ion storage layer contains a color-changing material opposite to each other showing a color reaction. do.

Electrochromic devices are one of the technologies that are attracting attention in the field of smart windows. A smart window is a window that can adjust the transmittance of visible light, infrared light, or ultraviolet light to suit the user's preference. Accordingly, when the smart window is applied to a vehicle or a building, not only aesthetics but also energy saving effect can be expected.

Meanwhile, one of the most important factors to commercialize the electrochromic element as a smart window is the durability of the electrochromic element. In order to improve the durability and reaction rate of the electrochromic device, studies on the introduction of a metal-organic compound, for example, a metallocene-based material, into the electrolyte layer have been widely reported at home and abroad.

The metallocene-based material serves to provide electrons to the reduced color change material when a voltage is applied to the electrochromic element. The reversible electron entry and exit of the metallocene-based material improves the durability and reaction speed of the electrochromic device. However, when the electrochromic element is exposed to moisture and atmospheric conditions, an irreversible oxidation reaction of the metallocene-based material proceeds. Accordingly, there is a problem in that the metallocene-based material is not free to enter and exit the electrochromic device durability, reaction rate, and storage stability of the electrolyte in a solution state also significantly reduced.

Accordingly, an object of the present application is to provide an electrochromic device that improves durability of the electrochromic device and storage stability of an electrolyte solution without deterioration of optical properties of the electrochromic device, in order to solve the conventional problems.

One aspect of the present application relates to an electrolyte composition.

In one example, an electrolyte component comprising an electrolyte; a resin component containing a curable resin; and an additive, wherein the additive provides an electrolyte composition comprising a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound.

In one example, the electrolyte may be any one of a liquid electrolyte, a polymer electrolyte, or an inorganic solid electrolyte.

In one example, the polymer electrolyte may include one or more repeating units of the following [Formula 1].

[Formula 1]

(R ₁ is an aromatic group, R ₂ is hydrogen or an alkali metal)

In one example, the weight average molecular weight of the polymer electrolyte may be in the range of 70,000 to 2.000.000.

In one example, the electrolyte component may further include an electrochromic material.

In one example, the electrochromic material is N,N,N',N'-tetramethylphenylenediamine, a viologen compound, a diphtahlocyanine compound, and a tetrathiafulvalene compound. It may include one or more selected from the group consisting of.

In one example, the concentration of the electrochromic material may be in the range of 0.01 mol to 1.0 mol based on 1 kg of the electrolyte component.

In one example, the electrolyte composition may include a photocurable water-based polymer electrolyte.

In one example, the curable resin component is a base resin; initiator; and a crosslinking agent.

In one example, the base resin may be a polymer including a polymerization unit of a (meth)acrylate monomer.

In one example, the initiator may be at least one selected from the group consisting of acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and triazine-based compounds.

In one example, the content of the initiator may be 0.1 to 5 mol% of the base resin.

In one example, the crosslinking agent may be a polymer including a polymerization unit of a (meth)acrylate monomer.

In one example, the content of the crosslinking agent may be 1 to 20 mol% of the base resin.

In one example, the metal organic compound may be a metallocene or a derivative thereof.

In one example, the content of the metal organic compound may be in the range of 0.025 to 0.1 wt% compared to the curable resin component.

In one example, the antioxidant may be a water-soluble antioxidant.

In one example, the content of the antioxidant may be in the range of 0.01 to 0.2 wt% compared to the curable resin component.

In one example, 50 to 90 parts by weight of an electrolyte component including an electrochromic material and an electrolyte; and 20 to 40 parts by weight of a resin component including a curable resin and an additive, wherein the additive provides an electrolyte composition comprising a metal organic compound and an antioxidant of the metal organic compound.

In one example, the metal organic compound may be metallocene, and the antioxidant of the metal organic compound may be ascorbic acid.

In one example, the pH of the electrolyte component may be in the range of 1.0 to 2.0.

Another aspect of the present application relates to an electrochromic device.

In one example, two electrode layers disposed opposite to each other; an electrolyte layer formed between the two electrodes; an electrochromic layer present between any one of the electrode layers and the electrolyte layer; and an ion storage layer present between the other one of the electrode layers and the electrolyte layer, wherein the electrolyte layer includes an electrolyte component including an electrolyte, a resin component including a curable resin, and an additive, wherein the additive includes It provides an electrochromic device comprising a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound.

According to an embodiment of the present application, an antioxidant for preventing irreversible oxidation of a metal-organic compound injected into the electrolyte layer to improve durability and reaction rate of the electrochromic element is introduced, thereby improving the optical properties of the electrochromic element. Durability can be improved without degradation. Furthermore, it is possible to improve the storage stability of the electrolyte solution, and thus the electrochromic device may have advantages in terms of marketability and process.

1 schematically illustrates an electrochromic device according to an embodiment of the present application.
2 illustrates a method of manufacturing an electrochromic device according to an embodiment of the present application.
3 is a graph measuring the transmittance per hour of the electrochromic device according to an embodiment of the present application, in which a) is Comparative Example 1 in which metallocene and antioxidants are not added, and b) is in which metallocene is added; This is the graph of Example 2.
4 is a graph showing transmittance at 650 nm per 250 repeated driving of the electrochromic device according to an embodiment of the present application. A) is Comparative Examples 1 and b) in which metallocene and antioxidants are not added. It is a graph of Comparative Example 2 in which metallocene was added.
5 is a graph showing transmittance at 650 nm per 1000 repeated driving of the electrochromic device according to an embodiment of the present application, a) is a comparative example 2 in which a metallocene is added, b) is a metallocene and It is a graph of Example 1 with the addition of antioxidants.
6 is a two-electrode cyclic voltammogram (CV) graph of an electrochromic device full-cell according to an embodiment of the present application, in Comparative Example 2 in which metallocene is added, and metallocene and antioxidant It is a graph of Example 1 with the addition of .
7 is a graph showing UV-vis spectroscopy of an electrolyte solution according to an embodiment of the present application, a) is a comparative example 2 in which a metallocene is added, b) is an example in which a metallocene and an antioxidant are added; 1 is a graph.
8 is a graph showing the transmittance per hour of the electrochromic device according to an embodiment of the present application according to 10 driving on the 1st day and 10 driving on the 6th day, a) is Comparative Example 2, b) in which metallocene is added; is a graph of Example 1 in which metallocene and antioxidants were added.
9 shows Comparative Example 2 in which an antioxidant was not added to the electrolyte solution according to an embodiment of the present application, Comparative Example 3 in which hydroquinone was added as an antioxidant, Comparative Example 4 in which gallic acid was added as an antioxidant, and L- According to the case of Example 1 in which ascorbic acid was added as an antioxidant, it shows the changes in the electrolyte solution by time (a) before the addition of the electrolyte, b) immediately after the addition of the electrolyte, c) after 1 day, d) after 5 days) .
10 shows the effect according to the content ratio of the antioxidant added to the electrolyte solution according to an embodiment of the present application, and a) shows when 0.11 wt% of L-ascorbic acid is added compared to the curable resin component. did it
11 shows Comparative Example 2 in which an antioxidant is not added to the electrolyte solution according to an embodiment of the present application, Example 2 in which 0.0125 wt% of L-ascorbic acid is added as an antioxidant compared to the electrolyte, 0.025 wt% is added Example 3, Example 4 with 0.0375 wt % added, and Example 5 with 0.05 wt % added (from left) a) immediately after addition, b) 1 day after, c) 2 days later, and d) 5 It shows the aspect of change over time after work.
12 is a graph showing transmittance loss (ΔT loss) over time of Comparative Examples 2, 2, 3, 4, and 5 of FIG. 11 .

Since the present application can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present application to specific embodiments, and it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present application. In describing the present application, if it is determined that a detailed description of a related known technology may obscure the gist of the present application, the detailed description thereof will be omitted.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

The terms used in the present application are used only to describe specific embodiments, and are not intended to limit the present application. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as “comprises” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Therefore, the configuration shown in the embodiment described in the present specification is only the most preferred embodiment of the present application and does not represent all the technical spirit of the present application, so various equivalents that can be substituted for them at the time of the present application and variations.

In addition, it should be understood that the accompanying drawings in the present application are enlarged or reduced for convenience of description.

Hereinafter, the present application will be described in more detail.

The present application, in one embodiment, an electrolyte component comprising an electrolyte; a resin component containing a curable resin; and an additive, wherein the additive provides an electrolyte composition comprising a metal organic compound and an antioxidant of the metal organic compound.

In addition, the electrolyte may be configured to provide electrolyte ions involved in the electrochromic reaction. Electrolyte ions are substances that can be involved in discoloration of the electrochromic layer, changes in optical properties of the device, cycle characteristics, and durability while repeating the process of being inserted and detached from the electrochromic layer when the electrochromic device is driven. The type of the electrolyte is not particularly limited, and may include an electrolyte composition that is any one of a liquid electrolyte, a polymer electrolyte, and an inorganic solid electrolyte. The electrolyte may be used in the form of a single layer or film so as to be laminated together with an adjacent layer configuration.

In one example, when the electrolyte is a liquid electrolyte, a solution in which a lithium salt such as LiOH or LiClO ₄ , a potassium salt such as KOH and a sodium salt such as NaOH are dissolved in a solvent may be used as the liquid electrolyte. However, the present invention is not limited thereto. The solvent may be at least one selected from the group consisting of propylene carbonate and ethylene carbonate, but is not limited thereto.

In another example, the polymer electrolyte may be an electrolyte composition including one or more repeating units of the following [Formula 1].

[Formula 1]

R ₁ is an aromatic group, and R ₂ is hydrogen or an alkali metal of Li, Na, or K.

In one example,

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 2] is poly(4-styrenesulfonic acid) (PSSA), [Formula 3] is poly(4-styrenesulfonic acid) lithium salt (PSSLi), and [Formula 4] is poly(4-styrenesulfonic acid) ) sodium salt (PSSNa). The polymer electrolyte of [Formula 2 to 4] has a hydrogen ion (H ⁺ ), a lithium ion (Li ⁺ ), or a sodium ion (Na ⁺ ) as a counter ion, respectively, in the sulfonic acid group of the styrenesulfonic acid repeating unit. It is a polymer material. Among these, poly(4-styrenesulfonic acid) (PSSA) of [Formula 2] is preferable from the viewpoint of having high ionic conductivity.

The weight average molecular weight (Mw) of the polymer electrolyte may be 70,000 to 2,000,000, 100,000 to 1,500,000, 300,000 to 1,200,000, or 500,000 to 1,000,000. The molecular weight may mean a value converted to standard polymethyl methacrylate or standard polystyrene measured by Gel Permeation Chromatography (GPC) or the like. The greater the molecular weight within the range of 70,000 to 2,000,000, the higher the ionic conductivity is, which is preferable.

The polymer electrolyte may be provided in the form of a solution containing a solid content. The solid content of the polymer electrolyte solution may be 1 to 50% by weight, 5 to 40% by weight, 10 to 30% by weight, 15 to 25% by weight, or 18 to 22% by weight. If the content of the polymer is less than 1% by weight, the ionic conductivity of the polymer electrolyte may be very poor, and if the content of the polymer exceeds 50% by weight, the solubility of the polymer electrolyte may decrease.

Polyelectrolyte has excellent ionic conductivity and transmittance, and has low haze, so it is considered as a suitable configuration for realizing light transmission characteristics of an electrochromic device. In addition, when a polymer electrolyte is used, it has a high viscosity unlike when lithium or sodium salt is used. This is unnecessary.

In another example, when the electrolyte is an inorganic solid electrolyte, the electrolyte may include lithium phosphorous oxynitride called LIPON (Lithium Phosphorous Oxynitride), or, for example, a transition such as Ta ₂ O ₅ . It may include an electrolyte in which lithium ions are doped into an oxide of a metal. Transition metals that can be used in the inorganic solid electrolyte include transition metals such as molybdenum (Mo), tantalum (Ta), zirconium (Zr), hafnium (Hf), and tungsten (W). When the inorganic solid electrolyte is used, there is no bubble generation even when the charge/discharge cycle is increased. Accordingly, there is no deterioration in durability of the electrochromic element, and lifespan can be increased.

On the other hand, the electrolyte composition of the present application is particularly suitable when applied to an electrochromic device. Accordingly, the electrolyte composition of the present application may further include an electrochromic material. Specifically, the electrolyte component of the electrolyte composition of the present application may further include an electrochromic material.

The electrochromic material may be selected from the group consisting of N,N,N',N'-tetramethylphenylenediamine, a viologen compound, a diphtahlocyanine compound, and a tetrathiafulvalene compound. It may include one or more selected.

The electrochromic material assists in a smooth redox reaction and improves electrochromic properties. In one example, N,N,N',N'-tetramethylphenylenediamine (TMPD) undergoes oxidative discoloration during reduction discoloration of the conductive polymer PEDOT-PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate). Electrochromic properties can be improved.

In this case, the content of the electrochromic material may also be appropriately adjusted. The concentration of the electrochromic material may be in the range of 0.01 mol to 1.0 mol based on 1 kg of the electrolyte component. More specifically, based on 1 kg of electrolyte component, 0.01 mol to 0.8 mol, 0.01 mol to 0.6 mol, 0.01 mol to 0.4 mol, 0.01 mol to 0.3 mol, 0.01 mol to 0.2 mol, 0.05 mol to 0.8 mol, 0.05 mol to 0.6 mol, 0.05 mol to 0.4 mol, 0.05 mol to 0.2 mol, 0.08 mol to 0.2 mol, or 0.09 mol to 0.15 mol. In the range of 0.01 mol to 1.0 mol per 1 kg of electrolyte component, even if the content of the electrochromic material increases, haze does not occur, and at the same time, the difference in transmittance before and after decolorization of the device (ΔT, to be described later [General Equation 1]) can be improved. In particular, when it is 0.1 mol or less per 1 kg, it is advantageous in terms of minimizing the amount of haze (Haze) generated.

In addition, the electrolyte composition may include a photocurable water-based polymer electrolyte.

The photocurable electrolyte can change a liquid electrolyte solution into a solid phase by irradiating light in the UV region. At this time, the coating method may be a doctor blade coating method, a slot die coating method, or a roll to roll coating method. The reason why the polymer electrolyte is water-based (water-soluble) is that polystyrene ends are sulfonated.

In one example, the photocurable aqueous polymer electrolyte composition is an aqueous type electrolyte composition that is dispersed in an aqueous solution rather than an organic solvent using a host polymer capable of imparting mechanical properties and a guest polymer serving as a hydrogen ion donor. , UV curing is possible. The host polymer refers to a base resin and a crosslinking agent that form a solid matrix by bonding with UV and an initiator. The guest polymer refers to a polymer electrolyte that provides ion conductivity.

The water-based electrolyte is eco-friendly because it does not use an organic solvent, and the concentration of hydrogen cations can be optimized by using a polymer electrolyte. Specifically, the concentration of cations in the electrolyte relative to the total amount can be increased by selectively adjusting the mass ratio of the solid content of the base resin and the polymer electrolyte (eg, 5:5, 4:6, or 3:7) according to the desired application field. . In addition, for the optimization of the hydrogen cation concentration, a water-soluble salt such as sulfuric acid, lithium salt, etc. may be additionally added.

For photocuring, a UV LED may be used as a UV light source. The wavelength of the ultraviolet light source may be 300 to 400 nm, 310 to 395 nm, 320 to 390 nm, 330 to 385 nm, 340 to 380 nm, 350 to 375 nm, or 360 to 370 nm.

The amount of UV light is 100 mW/cm2 or more (based on powerpuck ll), specifically 100 to 1,000 mW/cm2, 120 to 900 mW/cm2, 140 to 800 mW/cm2, 160 to 700 mW/cm2, 180 to 600 mW/cm2 cm 2 , or 200 to 500 mW/cm 2 .

The UV irradiation time may be 1 to 60 seconds, 3 to 50 seconds, 5 to 40 seconds, 7 to 30 seconds, or 10 to 20 seconds.

On the other hand, the curable resin component is a base resin; initiator; and a crosslinking agent.

More specifically, the base resin may act as a host polymer, and specifically may be a polymer including a polymerization unit of a (meth)acrylate monomer. That is, it may be a single molecule and/or a polymer having one or more (meth)acrylate groups.

In one example, poly(ethylene glycol) methacrylate or acrylamide may be used. However, as long as it is a known material that can be used as the base resin, it is not limited to the above material.

The mass ratio (A:P) of the base resin (A) to the polymer electrolyte (P) is 8:2 to 2:8, 7:3 to 2:8, 6:4 to 2:8, 5: 5 to 2:8, or 5:5 to 3:7. The higher the ratio of the polymer electrolyte, the higher the ionic conductivity is, so it is preferable.

On the other hand, the initiator (initiator) is a material that forms a radical (radical) upon UV irradiation, and may be at least one selected from the group consisting of acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and triazine-based compounds.

More specifically, examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-2-methyl-1-[2]. -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one , 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one oligomer etc. are mentioned.

More specifically, examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

More specifically, as a benzophenone-based compound, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

More specifically, the thioxanthone-based compound includes 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned.

More specifically, as the triazine-based compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2) -yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine;

In this case, the content of the initiator may be 0.1 to 5 mol%, 0.2 to 4 mol%, 0.4 to 3 mol%, 0.6 to 2 mol%, or 0.8 to 1.2 mol% of the base resin.

In addition, the cross-linker can act as a host polymer, control reaction rate and degree of curing, and provide excellent ionic conductivity due to excellent durability. The crosslinking agent may be a polymer including a polymerization unit of a (meth)acrylate monomer. That is, it may be a single molecule and/or a polymer having one or more acrylate groups.

In one example, the crosslinking agent is ethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate 1,6-hexanediol di(meth)acrylate, tri(propylene glycol) di(meth) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, One or more mixtures selected from the group consisting of dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. It can be used, but is not limited thereto.

The crosslinking agent content may be 1 to 20 mol%, 2 to 18 mol%, 4 to 16 mol%, 6 to 14 mol%, or 8 to 12 mol% of the base resin.

Meanwhile, the metal organic compound of the additive may be a metallocene or a derivative thereof.

The metal-organic chemical is a compound having at least one chemical bond between a carbon atom of an organic molecule and a metal, and in the present application, it may be a metallocene or a derivative thereof.

The metallocene has a structure in which a metal (M) is sandwiched between two cyclopentadienyl anions. More specifically, as the type of the metal, in addition to iron (Fe), various metal materials (M=Ti, V, Cr, Co, Ni, Ru, Os, Pd, etc.) may be used, and the metal is iron (Fe). The metallocene is Ferrocene.

In addition, the derivative of the metallocene, more specifically, ferrocene (ferrocene), methyl ferrocene (Methylferrocene), dimethyl ferrocene (Dimethylferrocene), acetyl ferrocene (Acethylferrocene), ethyl ferrocene (Ethylferrocene), vinyl ferrocene (Vinylferrocene), di At least one metal selected from the group consisting of phenylferrocene, methoxy-methylferrocene, butylferrocene, t-butylferroce, or chloromethyl ferrocene It may be a derivative of sen, but is not limited thereto.

On the other hand, the metal organic compound is oxidized and reduced in the opposite direction to the electrochromic material, thereby balancing the change in the amount of electric charge, so that the redox of the electrochromic material is smoothly performed. That is, when the electrochromic material is oxidized by providing electrons, the metal organic compound may be reduced by receiving electrons. Conversely, when the electrochromic material receives electrons and is reduced, the metal organic compound may be oxidized by providing electrons.

In one example, ferrocene, which is mainly used as the metal organic compound, is oxidized when a voltage is applied to contribute to discoloration to a cation (Fc ⁺ ) state. Accordingly, the electrochromic device including the metal organic compound may have improved electrochromic properties. Specifically, in the electrochromic device, the amount of change in transmittance may be increased even when the applied voltage is decreased. That is, the electrochromic device including the electrolyte containing the ferrocene (Fc) may exhibit excellent electrochromic properties even under a low voltage condition.

At this time, the content of the metal organic compound included in the additive in the present application may be in the range of 0.025 to 0.1 wt% compared to the curable resin component. More specifically, 0.025 to 0.09wt%, 0.025 to 0.08wt%, 0.025 to 0.07wt%, 0.025 to 0.06wt%, 0.03 to 0.08wt%, 0.03 to 0.06wt%, 0.04 to 0.08wt% or 0.04 to 0.06wt% % can be within the range. Although the optimum content ratio may vary within the above range depending on the composition of the electrolyte component, when the metal-organic compound exceeds 0.1 wt%, the initial transmittance (discoloration state) decreases, and solubility in the electrolyte component and the resin component There may be problems with downgrades.

However, immediately before coating the additive containing the metal organic compound, the resin component containing the curable resin, and the electrolyte component containing the electrolyte in the form of one layer or film so as to be laminated together with the adjacent layer configuration Upon mixing, irreversible oxidation of the metal organic compound occurs due to the high acidity of the electrolyte component.

Accordingly, the additive may include an antioxidant for preventing irreversible oxidation of the metal organic compound. The antioxidant may be a water-soluble antioxidant, and may be ascorbic acid.

In addition, the content of the antioxidant may be in the range of 0.01 to 0.2 wt% compared to the curable resin component. More specifically, the content of the antioxidant is 0.03 to 0.15 wt%, 0.05 to 0.15 wt%, 0.55 to 0.15 wt%, 0.03 to 0.13 wt%, 0.03 to 0.11 wt%, 0.05 to 0.13 wt%, 0.05 to 0.11 wt%, or 0.055 to 0.11 wt%. Preferably, the content of the antioxidant is higher in the range of 0.055 to 0.11 wt% compared to the curable resin component, the higher the irreversible antioxidant effect of the metal organic compound, and the lower the content of the metal organic compound, the lower the irreversible antioxidant effect of the metal organic compound. . In addition, when the content of the antioxidant is 0.11 wt % or more compared to the curable resin component, the curing problem of the resin occurs within a few hours, and the properties of the device are deteriorated.

On the other hand, the present application, in one embodiment, 50 to 90 parts by weight of an electrolyte component including an electrochromic material and an electrolyte; and 20 to 40 parts by weight of a resin component including a curable resin and an additive, wherein the additive provides an electrolyte composition comprising a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound.

That is, there is provided a two-component electrolyte composition including an electrolyte component including the electrochromic material and an electrolyte, and a resin component including a curable resin and an additive.

Here, in the two-component electrolyte composition, the electrolyte component including the electrochromic material and the electrolyte may include 50 to 90 parts by weight relative to the electrolyte composition. More specifically, 50 to 85 parts by weight, 50 to 80 parts by weight, 50 to 75 parts by weight, 50 to 70 parts by weight, 55 to 90 parts by weight, 55 to 80 parts by weight, 55 to 70 parts by weight, 60 parts by weight relative to the electrolyte composition to 90 parts by weight, 60 to 80 parts by weight, or 60 to 70 parts by weight. As the number of electrolyte components increases, the concentration of electrolyte ions increases, and there are advantages such as reaction rate, optical properties (ΔT), and durability improvement. On the other hand, as the number of electrolyte components increases, curability decreases and thus it cannot function as a solid electrolyte.

In addition, in the two-component electrolyte composition, the resin component including the curable resin and the additive may include 20 to 40 parts by weight relative to the electrolyte composition. More specifically, 20 to 37 parts by weight, 20 to 34 parts by weight, 23 to 40 parts by weight, 23 to 37 parts by weight, 23 to 34 parts by weight, 26 to 40 parts by weight, 26 to 35 parts by weight, 29 compared to the electrolyte composition to 35 parts by weight or 31 to 33 parts by weight. As the amount of the resin component increases, curability is improved, thereby preventing electrolyte leakage.

In other words, the ratio (A/(B+C)) between the weight (A) of the electrolyte component, the weight (B) of the resin component, and the weight (C) of the additive may be in the range of 1 to 5. However, the ratio of the electrolyte component and the resin component may vary depending on the type of the electrolyte or resin, which may vary depending on the viscosity of the electrolyte and the resin, the ion mobility/conductivity of the electrolyte, or the curability of the resin. can

In the two-component electrolyte composition, the pH of the electrolyte component including the electrochromic material and the electrolyte may be in the range of 1.0 to 2.0. More specifically, it may be in the range of pH 1.0 to 1.8, pH 1.0 to 1.6, pH 1.0 to 1.4, or pH 1.0 to 1.2. The pH of the electrolyte component including the electrochromic material and the electrolyte may be adjusted according to the input amount of the H ⁺ type electrolyte.

The two-component electrolyte composition, the electrolyte component and the resin component, are mixed just before coating in the form of one layer or film so that they can be laminated together with the adjacent layer composition. More specifically, in order to prevent oxidation of the metal organic compound of the resin component due to the low pH of the electrolyte component, it is preferable to prepare a two-component electrolyte composition and mix it immediately before coating.

On the other hand, the present application, in one embodiment, two electrodes disposed opposite; an electrolyte layer formed between the two electrodes; an electrochromic layer present between any one of the electrodes and the electrolyte layer; and an ion storage layer present between the other one of the electrodes and an electrolyte layer, wherein the electrolyte layer includes an electrolyte component including an electrolyte, a resin component including a curable resin, and an additive, wherein the additive comprises: It provides an electrochromic device comprising a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound.

The electrode layer may refer to a configuration capable of supplying electric charge to the electrochromic layer. In one example, it may be a transparent electrode or a reflective electrode.

The transparent electrode may include a transparent conductive compound (TCO); conductive polymers; silver nanowires; and at least one selected from the group consisting of a metal mesh. More specifically, ITO (Indium Tin Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminum doped Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), IZO (Indium doped Zinc Oxide) , at least one transparent conductive compound (TCO) selected from the group consisting of Niobium doped Titanium Oxide (NTO), Zinc Oxide (ZnO), Oxide/Metal/Oxide (OMO), and Cadmium Tin Oxide (CTO); conductive polymers; silver nanowires; and a metal mesh may be used as the electrode material, but the type of material forming the electrode layer is not particularly limited as long as it has conductivity to function as an electrode. In another example, the electrode layer may have a structure in which two or more electrode materials are stacked in a plurality of layers.

Here, the conductive polymer is CMC (carboxymethyl cellulose), PEDOT-PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), PEDOT-PANI (poly(3,4-ethylenedioxythiophene) polyaniline), EDOT (Ethylenedioxythiophene), CNT (Carbon) Nano Tube), PVDF (polyvinylidene fluoride), PEDOT: PPy, and may include one or more selected from the group consisting of SBR resin.

In particular, CMC (carboxymethyl cellulose), PEDOT-PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), or PEDOT-PANI has higher electrical conductivity than other conductive polymers. Therefore, they facilitate the movement of electrons between the color-changing materials, and accordingly, the ionic conductivity increases, and as a result, the effect of increasing the color-changing speed can be obtained.

A method of forming the electrode layer is not particularly limited, and a known method may be used without limitation. For example, the electrode layer may be provided by forming an electrode material including transparent conductive oxide particles on a transparent glass substrate in the form of a thin film through a sputtering process.

The thickness of the electrode layer is not particularly limited, but considering flexibility or interlayer adhesion, for example, the transparent electrode may have a thickness in the range of 1 nm to 1 μm. The electrode layer may have a thickness of 1 nm or more, 150 nm or more, or 300 nm or more within the range of 1 nm to 1 μm. The upper limit of the thickness of the electrode layer is not particularly limited, but the electrode layer may have a thickness of 800 nm or less, 700 nm or less, or 500 nm or less to realize low resistance.

In addition, the electrode layer may have a transmittance of 70% to 95% of visible light. "Transmittance" means the transmittance with respect to visible light of the electrochromic layer having a layer configuration described in the present application. Transmittance can be measured using known devices and methods. For example, a known device such as a Solidspec 3700 or an ellipsometer may be used to measure the transmittance of the electrochromic layer. In this case, the visible light may refer to light having a wavelength range of about 350 nm to 750 nm, and more specifically, light having a wavelength of 550 nm.

Meanwhile, an electrolyte layer is formed between the two electrode layers, and the electrolyte layer includes an electrolyte component including an electrolyte, a resin component including a curable resin, and an additive, wherein the additive is a metal organic compound and the metal organic compound contains antioxidants.

The thickness of the wet state of the electrolyte layer is in the range of 300 to 500㎛. More specifically, it may be in the range of 300 to 450 μm, 300 to 420 μm, 350 to 500 μm, 380 to 500 μm, 350 to 450 μm, or 380 to 430 μm. When the coating thickness is thin, the reaction rate is fast, but the leakage current increases and the durability tends to decrease. Conversely, as the coating thickness increases, the reaction rate tends to decrease.

The electrolyte layer may have a light transmittance of 70% to 95% for visible light. More specifically, the light transmittance in visible light may range from 75% to 95%, 85% to 95%, 90% to 95%, 70% to 80%, or 70% to 90%. In this case, the visible light may refer to light having a wavelength range of about 350 nm to 750 nm, and more specifically, light having a wavelength of 550 nm.

In addition, since the electrolyte layer is the same as the above detailed description, it will be omitted.

On the other hand, an electrochromic layer existing between the other one of the electrode layers and the electrolyte layer is included. The electrochromic layer may include an electrochromic material whose color is changed by being colored or discolored by application of a voltage. The electrochromic layer may include at least one metal oxide selected from the group consisting of Cr, Mn, Fe, Co, Ni, Li, Rh, Ir, Ti, Nb, Mo, V, Ta and W.

In one example, the electrochromic layer is an oxidative electrochromic material Cr, Mn, Fe, Co, Ni, Li, Rh, Ir, Ti, Nb, Mo, V, Ta and at least one metal selected from the group consisting of W Oxides may be included. The oxidative discoloration material refers to a material exhibiting low light transmittance while discoloration (coloring) occurs during an oxidation reaction according to voltage application. The oxidative discoloration material exhibits high light transmittance while discoloration (discoloration) occurs during the reduction reaction.

In one example, the electrochromic layer may include one or more oxides selected from the group consisting of Ti, Nb, Mo, V, Ta, and W, which are reducing electrochromic materials. The reductive discoloration material refers to a material that exhibits low light transmittance while discoloration (coloring) occurs during a reduction reaction according to voltage application. The reducible color-changing material exhibits high light-transmitting properties while discoloration (discoloration) occurs during an oxidation reaction.

In addition, the electrochromic layer may be an electrochromic device satisfying ΔT≥30 of the following [General Formula 1]. :

[General formula 1]

(T _a is the transmittance of visible light when the electrochromic layer is discolored, T _b is the transmittance of visible light when the electrochromic layer is colored)

The electrochromic layer according to the present application has a difference in transmittance for visible light when the light transmittance of the device is bleached and the transmittance for visible light when the light transmittance of the device is colored in [General Formula 1]. is configured to satisfy at least 30% or more. More specifically, it may be 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, or 60% or more.

On the other hand, it includes an ion storage layer existing between the other one of the electrode layer and the electrolyte layer.

The ion storage layer may refer to a layer formed to balance charge with the electrochromic layer during a reversible redox reaction for discoloration of the electrochromic material. More specifically, the ion storage layer may refer to a layer capable of participating in the color change reaction because charged particles necessary for the redox reaction of the electrochromic layer may be inserted or desorbed.

The ion storage layer may include one or more metal oxides selected from the group consisting of Cr, Mn, Fe, Co, Ni, Li, Rh, Ir, Ti, Nb, Mo, V, Ta and W.

In one example, in order to balance the charge between the electrochromic layer and the ion storage layer, a complementary electrochromic material may be used for each of the electrochromic layer and the ion storage layer. Accordingly, when the electrochromic layer contains an oxidative color-changing material such as lithium nickel oxide (LiNiOx), the ion storage layer may include a reducing color-changing material such as tungsten oxide (WOx).

The thickness of the ion storage layer is not particularly limited. For example, the thickness of the ion storage layer may be 1 μm or less. Specifically, the thickness may be 50 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more, and may be 900 nm or less, 700 nm or less, 500 nm or less, or 400 nm or less.

Hereinafter, the present application will be described in detail through examples. However, the protection scope of the present application is not limited by the examples described below.

Example

Example 1

After the electrolyte composition is prepared in a two-component form of an electrolyte component and a resin component, the two-component electrolyte composition is mixed immediately before coating.

One) Preparation of Electrolyte Components

The weight average molecular weight (Mw) is 500,000, based on 1 kg of poly(4-styrenesulfonic acid) having H ⁺ as a counter ion (PSSA, Formula 2) and polyelectrolyte in the form of a solution containing 20% by weight of a solid content An electrolyte component is prepared by mixing mol of N,N,N',N'-tetramethylphenylenediamine (N,N,N,N-Tetramethyl-p-phenylenediamine, TMPD) as an electrochromic material.

2) Preparation of resin components

The resin component includes a curable resin and an additive.

The curable resin includes a base resin, an initiator, and a crosslinking agent. In this experiment, poly(ethylene glycol) was used as the base resin. The mass ratio (A:P) of the base resin (A) to the polymer electrolyte (P) was 7:3 based on the solid content.

1-Hydroxy-cyclohexyl-phenyl-ketone was used as the initiator. The content of the initiator was 1 mol% of the base resin.

Poly(ethylene glycol) diacrylate was used as a crosslinking agent. The content of the crosslinking agent was 10 mol% of the base resin.

In addition, the additive includes a metal organic compound and an antioxidant.

The metallocene used as the metal organic compound was ferrocene, and ferrocene having a content of 0.05 wt% compared to the curable resin was used.

As the antioxidant, L-ascorbic acid having a content of 0.055 wt% compared to the curable resin was used.

3) Mixing the electrolyte composition of 1) and the resin component of 2)

The electrolyte composition of 1) and the resin component of 2) are mixed in a ratio of 67.5 parts by weight and 32.5 parts by weight.

Example 2

An electrolyte composition was prepared in the same manner as in Example 1, except that L-ascorbic acid having an antioxidant content of 0.0125 wt% compared to the electrolyte was used.

Example 3

An electrolyte composition was prepared in the same manner as in Example 1, except that L-ascorbic acid having an antioxidant content of 0.025 wt% compared to the electrolyte was used.

Example 4

An electrolyte composition was prepared in the same manner as in Example 1, except that L-ascorbic acid having an antioxidant content of 0.0375 wt% compared to the electrolyte was used.

Example 5

An electrolyte composition was prepared in the same manner as in Example 1, except that L-ascorbic acid having an antioxidant content of 0.05 wt% compared to the electrolyte was used.

Comparative Example 1

An electrolyte composition was prepared in the same manner as in Example 1, except that metallocene and antioxidants were not added.

Comparative Example 2

An electrolyte composition was prepared in the same manner as in Example 1 except that an antioxidant was not added.

Comparative Example 3

An electrolyte composition was prepared in the same manner as in Example 1, except that hydroquinone, not L-ascorbic acid, was added as an antioxidant.

Comparative Example 4

An electrolyte composition was prepared in the same manner as in Example 1, except that gallic acid, not L-ascorbic acid, was added as an antioxidant.

Experimental example

One. Manufacturing of electrochromic device

For the manufacture of the electrochromic device, the specimen was manufactured in the following order with reference to FIG. 2 showing a method of manufacturing the electrochromic device according to an embodiment of the present application.

1) On a PET substrate having a size of 5 cm × 5 cm, a conductive polymer (PEDOT:PSS) is applied using a wire bar coater of RDS Corporation using No. 40 bar for the working electrode and No. 15 bar for the counter electrode.

2) Then, by using an oven to dry at a temperature of about 150° C. for about 4 minutes, the conductive polymer (PEDOT:PSS) is prepared to have a thickness of about 500 nm at the working electrode and about 150 nm at the counter electrode [1 in FIG. 2) See PEDOT:PSS Bar Coating].

3) The electrolyte composition prepared in the above embodiment is applied on the layer coated with the conductive polymer solution of the working electrode, and then coated so that the coating thickness is about 400 nm using the blade coating method. Next, an electrolyte is formed by irradiating an ultraviolet light source (UV LED) with a wavelength of 365 nm, light quantity of 200 mW/cm 2 or more (based on powerpuck ll), irradiation time of 10 to 20 seconds, and the distance between the light source and the coating layer is 7.5 cm [Fig. See 2) Electrolytic Blade Coating in 2].

4) A counter electrode is manufactured in the same manner as in 1), and after complete curing, the layer coated with the conductive polymer solution of the counter electrode and the electrolyte layer are laminated in contact with each other by applying pressure [see 3 in FIG. 2) Lamination ].

5) in the same manner as above, as shown in FIG. 1, two electrode layers 11 facing each other; an electrolyte layer 13 formed between the two electrodes; an electrochromic layer 12 present between any one of the electrode layers and the electrolyte layer; and an ion storage layer 14 present between the other one of the electrode layers and the electrolyte layer, wherein the electrolyte layer includes an electrolyte component including an electrolyte, a resin component including a curable resin, and an additive, The additive was prepared as an electrochromic device 10 including a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound.

2. Transmittance measurement

A method of preparing a sample for measuring transmittance according to the present application is as follows.

1) A PET film (5 cm × 5 cm) having a thickness of 100 μm was prepared.

2) The electrolyte composition was coated on PET to a thickness of 300 μm using a doctor blade (coating speed: 10 mm/sec).

3) Using a UV irradiation device (Limtech Co., Ltd. LGA-15200F, UV LED intensity of 200 mW/cm 2 and output 20%), UV was irradiated for 10 seconds to cure (electrolyte film thickness after curing: 150 μm).

4) The transmittance was measured using UV-vis-NIR spectrophotometry (JASCO Corporation, V-650) (wavelength range: 200 nm to 1,100 nm).

3. Evaluation

3 is a graph measuring the transmittance per hour of the electrochromic device according to an embodiment of the present application, in which a) is Comparative Example 1 in which metallocene and antioxidants are not added, and b) is in which metallocene is added; This is the graph of Example 2.

3 b) Referring to the graph of Comparative Example 2, when metallocene was added, it was found that the decolorization rate was improved without a significant drop in ΔT compared to a) Comparative Example 1 in which the metallocene was not added.

4 is a graph showing transmittance at 650 nm per 250 or more repeated driving of the electrochromic device according to an embodiment of the present application; is a graph of Comparative Example 2 in which metallocene was added. More specifically, discoloration was performed for 30 seconds at a driving voltage of 1.2V, and decolorization was performed for 120 seconds at a driving voltage of 0V, and transmittance was measured under the same conditions.

4 b) Referring to the graph of Comparative Example 2, it was found that when metallocene was added, durability was superior to that of Comparative Example 1 a) in which metallocene was not added.

5 is a graph showing transmittance at 650 nm per 1000 repeated driving of the electrochromic device according to an embodiment of the present application, a) is a comparative example 2 in which a metallocene is added, b) is a metallocene and It is a graph of Example 1 with the addition of antioxidants. More specifically, discoloration was performed for 30 seconds at a driving voltage of 1.2V, and decolorization was performed for 120 seconds at a driving voltage of 0V, and transmittance was measured under the same conditions.

Referring to the graph of b) Example 1 of FIG. 5 , it was found that when the metallocene and the antioxidant were added, the durability was superior to that of Comparative Example 2 a) in which only the metallocene was added.

6 is a two-electrode cyclic voltammogram (CV) graph of an electrochromic device full-cell according to an embodiment of the present application, in Comparative Example 2 in which metallocene is added, and metallocene and antioxidant; It is a graph of Example 1 with the addition of .

Referring to FIG. 6 , it was confirmed that there was almost no change in the electrochemical properties of the electrochromic device according to the presence or absence of the addition of antioxidant.

7 is a graph showing UV-vis spectroscopy of an electrolyte solution according to an embodiment of the present application, a) is a comparative example 2 in which a metallocene is added, b) is an example in which a metallocene and an antioxidant are added; 1 is a graph.

Since ferrocene used in the experiment changes color from yellow to blue when irreversible oxidation occurs, the degree of irreversible oxidation can be determined through the color change of the solution phase over time.

Therefore, referring to the peak change rates in a) and b) of FIG. 7 , it can be seen that the antioxidant inhibits the irreversible oxidation of metallocene (ferrocene).

8 is a graph showing the transmittance per hour of the electrochromic device according to an embodiment of the present application according to 10 driving on the 1st day and 10 driving on the 6th day, a) is Comparative Example 2, b) in which metallocene is added; is a graph of Example 1 in which metallocene and antioxidants were added.

Referring to the graph of Example 1 in b) of FIG. 8 , it was found that when the metallocene and the antioxidant were added, the durability was superior to that of Comparative Example 2 a) in which only the metallocene was added.

9 shows Comparative Example 2 in which an antioxidant was not added to the electrolyte solution according to an embodiment of the present application, Comparative Example 3 in which hydroquinone was added as an antioxidant, Comparative Example 4 in which gallic acid was added as an antioxidant, and L- According to the case of Example 1 in which ascorbic acid was added as an antioxidant, it shows the changes in the electrolyte solution by time (a) before the addition of the electrolyte, b) immediately after the addition of the electrolyte, c) after 1 day, d) after 5 days) .

Referring to c) and d) of FIG. 9 , after several days have elapsed, Comparative Example 2 in which no antioxidant was added, Comparative Example 3 in which hydroquinone was added as an antioxidant, and Comparative Example 4 in which gallic acid was added as an antioxidant were yellow. It can be seen that irreversible oxidation has occurred as the color change from blue to blue has occurred. On the other hand, only in the case of Example 1 in which L-ascorbic acid was added as an antioxidant, no color change to blue was observed, indicating that the irreversible oxidation was inhibited by L-ascorbic acid.

10 shows the effect according to the content ratio of the antioxidant added to the electrolyte solution according to an embodiment of the present application, and a) shows when 0.11 wt% of L-ascorbic acid is added compared to the curable resin component. did it

Referring to FIG. 10 a), it can be seen that when 0.11 wt% or more of L-ascorbic acid is added compared to the curable resin component (0.05 wt% compared to electrolyte), curing problems occur within several hours.

11 shows Comparative Example 2 in which an antioxidant is not added to the electrolyte solution according to an embodiment of the present application, Example 2 in which 0.0125 wt% of L-ascorbic acid is added as an antioxidant compared to the electrolyte, 0.025 wt% is added Example 3, Example 4 with 0.0375 wt % added, and Example 5 with 0.05 wt % added (from left) a) immediately after addition, b) 1 day after, c) 2 days later, and d) 5 It shows the aspect of change over time after work.

12 is a graph showing transmittance loss (ΔT loss) according to time of Comparative Example 2, Example 2, Example 3, Example 4, and Example 5 of FIG. 11 . The transmittance loss was derived according to the following [General Formula 2].

[General formula 1]

Here, T _a is the transmittance of visible light when the electrochromic layer is decolorized, and T _b is the transmittance of visible light when the electrochromic layer is colored.

[General formula 2]

는 2회 구동에서의 투과율,

은 10회 구동에서의 투과율 값이다.here,

is the transmittance in two runs,

is the transmittance value at 10 runs.

content ratio 1 day later 2 days later 3 days later Comparative Example 2 (0 wt%) 1.5 5.4 10.4 Example 2 (0.0125 wt%) 3.4 1.0 6.6 Example 3 (0.025 wt%) 2.3 2.6 2.9 Example 4 (0.0375 wt%) -0.3 0.3 11.1 Example 5 (0.05 wt%) -1.4 0.3 8.4

Referring to [Table 1] and [Fig. 12], it can be seen that Example 3 in which 0.025 wt% of L-ascorbic acid was added as an antioxidant compared to the electrolyte had the best antioxidant effect. On the other hand, when 0.0125 wt% or less of L-ascorbic acid is added as an antioxidant compared to the electrolyte, the antioxidant effect is reduced.

In addition, it can be seen that when 0.0375wt% or more of L-ascorbic acid is added as an antioxidant compared to the electrolyte, device characteristics are deteriorated.

10: electrochromic element
11: electrode layer
12: electrochromic layer
13: electrolyte layer
14: ion storage layer

Claims (22)

An electrolyte composition for forming an electrolyte layer, comprising:
an electrolyte component comprising an electrolyte;
a resin component containing a curable resin; and
containing additives;
The additive includes a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound,
the antioxidant is ascorbic acid,
The content of the antioxidant is in the range of 0.013 to 0.037 wt% of the curable resin component, the electrolyte composition. The method of claim 1,
The electrolyte is any one of a liquid electrolyte, a polymer electrolyte, or an inorganic solid electrolyte.
3. The method of claim 2,
The polymer electrolyte is an electrolyte composition comprising one or more repeating units of the following [Formula 1].
[Formula 1]

(R ₁ is an aromatic group, R ₂ is hydrogen or an alkali metal)
3. The method of claim 2,
The weight average molecular weight of the polymer electrolyte is in the range of 70,000 to 2,000,000 electrolyte composition. The method of claim 1,
The electrolyte composition further comprises an electrochromic material.
6. The method of claim 5,
The electrochromic material may be selected from the group consisting of N,N,N',N'-tetramethylphenylenediamine, a viologen compound, a diphtahlocyanine compound, and a tetrathiafulvalene compound. Electrolyte composition comprising one or more selected.
6. The method of claim 5,
The concentration of the electrochromic material is in the range of 0.01 mol to 1.0 mol, based on 1 kg of the electrolyte component.
The method of claim 1,
The electrolyte composition is an electrolyte composition comprising a photocurable water-based polymer electrolyte.
The method of claim 1,
The curable resin component is a base resin; initiator; and an electrolyte composition comprising a crosslinking agent.
10. The method of claim 9,
The base resin is an electrolyte composition comprising a polymer unit of a (meth) acrylate monomer.
10. The method of claim 9,
The initiator is at least one electrolyte composition selected from the group consisting of acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and triazine-based compounds.
10. The method of claim 9,
The content of the initiator is 0.1 to 5 mol% of the base resin electrolyte composition.
10. The method of claim 9,
The crosslinking agent is an electrolyte composition comprising a polymer unit of a (meth) acrylate monomer.
10. The method of claim 9,
The content of the crosslinking agent is 1 to 20 mol% of the base resin electrolyte composition.
The method of claim 1,
wherein the metal organic compound is a metallocene or a derivative thereof.
The method of claim 1,
The content of the metal organic compound is in the range of 0.025 to 0.1wt% of the curable resin component, the electrolyte composition.
The method of claim 1,
wherein the antioxidant is a water-soluble antioxidant.
delete An electrolyte composition for forming an electrolyte layer, comprising:
50 to 90 parts by weight of an electrolyte component including an electrochromic material and an electrolyte; and
20 to 40 parts by weight of a resin component including a curable resin and additives,
The additive includes a metal organic compound and an antioxidant of the metal organic compound,
the antioxidant is ascorbic acid,
The content of the antioxidant is in the range of 0.013 to 0.037 wt% of the curable resin component, the electrolyte composition. 20. The method of claim 19,
The metal organic compound is an electrolyte composition of metallocene. 20. The method of claim 19,
The pH of the electrolyte component is in the range of 1.0 to 2.0 electrolyte composition.
two electrode layers facing each other;
an electrolyte layer formed between the two electrodes;
an electrochromic layer present between any one of the electrode layers and the electrolyte layer; and
An ion storage layer present between the other one of the electrode layers and the electrolyte layer,
The electrolyte layer includes an electrolyte component including an electrolyte, a resin component including a curable resin, and an additive, wherein the additive includes a metal organic compound and an antioxidant for preventing oxidation of the metal organic compound,
the antioxidant is ascorbic acid,
The content of the antioxidant is in the range of 0.013 to 0.037 wt% compared to the curable resin component of the electrochromic device.

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