KR20190004033A - Electrochromism element - Google Patents

Abstract

The present invention relates to an electrochromic device capable of providing an electrolyte layer that cannot be transferred or expanded toward a transparent electrode. The electrochromic device according to an embodiment of the present invention comprises: a first substrate; a first electrode disposed on the first substrate; a first chromic material layer disposed on the first electrode and including a first chromic material; an electrolyte layer disposed on the first chromic material layer; a second chromic material layer disposed on the electrolyte layer and including a second chromic material; a second electrode disposed on the second chromic material layer; and a second substrate disposed on the second electrode, wherein at least one of the first substrate and the second substrate is a transparent substrate, at least one of the first electrode and the second electrode is a transparent electrode, and the electrolyte layer includes at least one of a polymerizable monomer, a polymerizable oligomer, and a polymer, a first ionic liquid, and a second ionic liquid that is different from the first ionic liquid. The first ionic liquid cannot react with at least one of the polymerizable monomer, the polymerizable oligomer, and the polymer and the second ionic liquid can react with at least one of the polymerizable monomer, the polymerizable oligomer.

Description

ELECTROCHROMISM ELEMENT [0001]

TECHNICAL FIELD The present invention relates to an electrochromic device, and more particularly, to an electrolyte layer included in an electrochromic device.

Electrochromism is a phenomenon in which the color reversibly changes in the direction of the electric field when a voltage is applied. A substance capable of reversibly changing the optical characteristics of the material by an electrochemical redox reaction having such characteristics is called an electrochromic material . Such an electrochromic material is not colored when an external electrical signal is not applied, is colored when an electrical signal is applied, or is colored when an external signal is not applied. The color disappears.

The electrochromic device is a device using a phenomenon in which the light transmittance of an electrochromic material is changed by an electrochemical redox reaction. The electrochromic device is a device for posting such as a display, a large poster or a signboard requiring a discoloration of a specific part such as an ESL (electro shelf label) It is used to control the light transmittance or reflectivity of smart windows, architectural window glasses, automobile mirrors, flexible displays, automobile sunroofs, sport glasses, etc. Recently, it has not only the color change in the visible light region but also the infrared ray blocking effect As a result, it has been attracting great attention for its applicability as an energy-saving product.

The performance of such an electrochromic device depends on the rate of discoloration, and the rate of discoloration can be influenced by the electrolyte. Accordingly, there has been an attempt to form an electrolyte using an ionic liquid in order to improve the discoloration rate. An ionic liquid means a salt in a liquid state, and the cation and the anion have a characteristic of being electrically neutral by making the charge of each other zero. BACKGROUND ART An ionic liquid has attracted attention as an electrolyte material because it has low vapor pressure, nonflammable, electrochemical stability and high ionic conductivity at room temperature.

When the ionic liquid is used solely as a material for the electrolyte, there is a limitation in processing of the film form and thinning of the color-changing element due to leakage of the electrolyte. In order to solve this problem, the ionic liquid may be mixed with the polymer and then cured using UV or heat. However, even in such a case, there is a problem that the electrolyte layer is transferred toward the transparent electrode after repeated driving.

SUMMARY OF THE INVENTION The present invention provides an electrolyte layer of an electrochromic device.

According to an embodiment of the present invention, an electrochromic device includes a first substrate, a first electrode disposed on the first substrate, a first color-change material layer disposed on the first electrode and including a first color-change material, An electrolyte layer disposed on the coloring material layer, a second color-change material layer disposed on the electrolyte layer and including a second color-change material, a second electrode disposed on the second color-change material layer, 2 substrate, at least one of the first substrate and the second substrate is a transparent substrate, at least one of the first electrode and the second electrode is a transparent electrode, and the electrolyte layer comprises a polymerizable monomer, Wherein the first ionic liquid comprises at least one of an oligomer and a polymer, a first ionic liquid, and a second ionic liquid that is different from the first ionic liquid, wherein the first ionic liquid comprises the polymerizable monomer, Wherein the second ionic liquid is an ionic liquid that is capable of reacting with at least one of the polymerizable monomer, the polymerizable oligomer, and the polymer.

The second ionic liquid may be an ionic liquid in which the cation comprises a carbon double bond or a carbon triple bond.

The second ionic liquid may be an ionic liquid in which the cation comprises a vinyl group or an acrylate group.

The second ionic liquid may be an ionic liquid in which the cation further comprises at least one of imidazolium or ammonium.

The second ionic liquid may be selected so that the cation is selected from the group consisting of 1-methyl-3-vinylimidazolium or [3- (methacryloylamino) propyl] trimethylammonium ([ methacryloylamino) propyl] trimethylammonium).

Wherein the first ionic liquid has a cation such that the cation is selected from the group consisting of ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, at least one of pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolium and thiazolium, and triazolium. One can be included.

The second ionic liquid may be included in an amount of 5 to 15 parts by weight based on 10 parts by weight of the first ionic liquid.

The electrolyte layer may further include a lithium salt.

The electrolyte layer may further include a photoinitiator.

According to an embodiment of the present invention, an electrochromic device includes a first substrate, a first electrode disposed on the first substrate, a first color-change material layer disposed on the first electrode and including a first color-change material, An electrolyte layer disposed on the coloring material layer, a second color-change material layer disposed on the electrolyte layer and including a second color-change material, a second electrode disposed on the second color-change material layer, 2 substrate, at least one of the first substrate and the second substrate is a transparent substrate, at least one of the first electrode and the second electrode is a transparent electrode, and the electrolyte layer comprises a polymerizable monomer, Wherein the first ionic liquid comprises at least one of an oligomer and a polymer, a first ionic liquid, and a second ionic liquid that is different from the first ionic liquid, wherein the first ionic liquid comprises the polymerizable monomer, Wherein the second ionic liquid is an ionic liquid which is not capable of reacting with at least one of an oligomer and a polymer, and the second ionic liquid is an ionic liquid capable of reacting with at least one of the polymerizable monomer, a polymerizable oligomer and a polymer, A first terminal portion connected to the electrode and having a first polarity, and a second terminal portion connected to the second electrode and having a second polarity.

According to the embodiment of the present invention, an electrochromic device having a high color fastness can be obtained. Particularly, according to the embodiment of the present invention, it is possible to obtain an electrolyte layer which does not transfer or diffuse toward the transparent electrode, while being capable of processing film form and thin film form with high discoloration rate and free from leakage.

1 is a cross-sectional view of an electrochromic device according to an embodiment of the present invention.
2 is a cross-sectional view of an electrochromic device according to another embodiment of the present invention.
3 is a cross-sectional view of an electrochromic device according to another embodiment of the present invention.
4 is a photograph of the electrolyte layer of Example 3 after repeated driving.
5 is a photograph of the electrolyte layer of Comparative Example 1 after repeated driving.

The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated and described in the drawings. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terms including ordinal, such as second, first, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the second component may be referred to as a first component, and similarly, the first component may also be referred to as a second component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

In describing embodiments, it is to be understood that each layer (film), area, pattern or structure may be referred to as being "on" or "under" a substrate, layer, Includes all that is formed directly or via another layer. The criteria for top / bottom or bottom / bottom of each layer are described with reference to the drawings. In addition, the thickness or size of each layer (film), region, pattern or structure in the drawings may be modified for clarity and convenience of explanation, and thus does not entirely reflect the actual size.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, wherein like or corresponding elements are denoted by the same reference numerals, and redundant description thereof will be omitted.

1 is a cross-sectional view of an electrochromic device according to an embodiment of the present invention.

1, the electrochromic device 100 includes a first electrode unit 110, a first coloring material layer 120 disposed on the first electrode unit 110 and including a first coloring material, An electrolyte layer 130 disposed on the material layer 120, a second color fading material layer 140 disposed on the electrolyte layer 130 and including a second color fading material, a second color fading material layer 140 disposed on the second color fading material layer 140, And a two-electrode unit 150. The first electrode unit 110 and the second electrode unit 150 are connected to the first terminal unit 160 and the second terminal unit 170 having different polarities and the first terminal unit 160 and the second terminal unit 170, As shown in Fig. A sealing portion 180 may be further disposed on a side surface of the first color discoloration material layer 120, the second color fading material layer 140, and the electrolyte layer 130.

The first electrode unit 110 includes a first transparent substrate 112 and a first transparent electrode 114 and the second electrode unit 150 includes a second transparent substrate 152 and a second transparent electrode 154).

Here, the first transparent substrate 112 and the second transparent substrate 152 are transparent substrates having a transmittance (T%) of 98% or more, and may be glass, plastic, or a flexible polymer film. For example, the flexible polymer film may be made of polyethylene terephthalate (PET), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polymethylmethacrylate (PEN), Polyether Sulfone (PES), Cyclic Olefin Copolymer (COC), TAC (Triacetylcellulose) film, polyvinyl alcohol (PEN) A polyvinyl alcohol (PVA) film, a polyimide (PI) film, and polystyrene (PS). However, the present invention is not limited thereto.

The first color-change material layer 120, the electrolyte layer 130, and the second color-change material layer 140 are reversibly changed in color by applying an external voltage using the principle of electrochromism, Or the element whose transmittance is changed. The total thickness of the first color-change material layer 120, the electrolyte layer 130 and the second color-change material layer 140 may be 10 to 500 μm, preferably 20 to 300 μm, more preferably 50 to 200 μm have. When the total thickness of the first color-change material layer 120, the electrolyte layer 130 and the second color-change material layer 140 is less than 10 mu m, the contact between the first transparent electrode 114 and the second transparent electrode 154 And when the total thickness of the first color-change material layer 120, the electrolyte layer 130 and the second color-change material layer 140 exceeds 500 mu m, the electrical conductivity decreases and the reaction rate Can be slowed down.

The first color decoloring material layer 120 and the second color decoloring material layer 140 may include materials having excellent discoloration or discoloration performance, excellent response speed, durability, and memory effect. For example, the first discoloration material layer 120 may be an oxidative discoloration layer that performs an oxidation reaction, and the second discoloration material layer 140 may be a reducing discoloration layer that performs a reducing reaction. Alternatively, the first color-change material layer 120 may be a reducing color-changing layer that performs a reduction reaction, and the second color-change material layer 140 may be an oxidative discoloration layer that performs an oxidation reaction.

The first color-change material layer 120 and the second color-change material layer 140 may include at least one of an organic-based discoloration material and an inorganic-based discoloration material. In the present specification, the discoloring substance means a substance having an electrochromic characteristic in which the light absorbance is changed by an electrochemical oxidation or reduction reaction, and reversibly changes the electrochemical oxidation of the electrochromic material depending on whether the voltage is applied or not, , A reduction phenomenon occurs, whereby the transparency and absorbance of the color-changing material can be reversibly changed. The organic discoloring materials may be selected from the group consisting of, for example, violenes, anthraquinones, polypyrroles and polythiophenes, polyanthracenes, polyfluorenes, polycarbazoles, polyphenylvinylenes and derivatives thereof, The discoloring material may be selected from the group consisting of, for example, oxides of tungsten, iridium, nickel, vanadium, molybdenum, manganese, titanium, cerium and niobium. Alternatively, the discoloring material may be Prussian blue (PB), PB analog (PBA). WO ₃ is a discoloring substance included in the reducing discoloration layer, and PB is a discoloring substance included in the oxidative discoloring layer.

In addition, each of the first transparent electrode 114 and the second transparent electrode 154 may include a transparent conductive material capable of flowing electricity without interfering with transmission of light. The transparent conductive material may be at least one selected from the group consisting of ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide), IZO (indium zinc oxide), copper oxide, zinc oxide, Of a metal oxide. Alternatively, the transparent conductive material may comprise a nanofowder composition such as a nanowire, a photosensitive nanowire film, a carbon nanotube (CNT), a graphene, or a mixture thereof. Here, it is possible to control the color and reflectance while securing the electric conductivity through controlling the content of the nano powder. Alternatively, the transparent conductive material may be at least one selected from the group consisting of Cr, Ni, Cu, Al, Ag, Mo, Au, Ti, And may include at least one. Each of the first transparent electrode 114 and the second transparent electrode 154 may be in the form of a film, and the transmittance to light may be 80% or more.

2 is a cross-sectional view of an electrochromic device according to another embodiment of the present invention. The description of the same components as those of FIG. 1 will not be repeated.

Referring to FIG. 2, the electrochromic device 100 includes a first electrode unit 110, a first coloring material layer 120 disposed on the first electrode unit 110 and including a first coloring material, An electrolyte layer 130 disposed on the material layer 120, a second color fading material layer 140 disposed on the electrolyte layer 130 and including a second color fading material, a second color fading material layer 140 disposed on the second color fading material layer 140, And a two-electrode unit 150. The first electrode unit 110 and the second electrode unit 150 are connected to the first terminal unit 160 and the second terminal unit 170 having different polarities and the first terminal unit 160 and the second terminal unit 170, As shown in Fig. A sealing portion 180 may be further disposed on a side surface of the first color discoloration material layer 120, the second color fading material layer 140, and the electrolyte layer 130.

The first electrode unit 110 includes a first transparent substrate 112 and a first transparent electrode 114 and the second electrode unit 150 includes a second transparent substrate 152 and a second transparent electrode 154).

According to an embodiment of the present invention, a substrate 200 having a predetermined color may be additionally disposed under the first electrode layer 110. Here, the predetermined color may be a white color, so that letters, numbers, pictures, and the like that are discolored may be displayed more clearly. Alternatively, the predetermined color may be various colors in addition to the white color. Depending on the color of the substrate 200, colors such as letters, numbers, and pictures that are discolored may be finely adjusted. According to the embodiment of the present invention, when an electrochromic device is applied to an electro-shelf label (ESL) display, a digital signage, an E-paper or the like, colors of letters, numbers, .

3 is a cross-sectional view of an electrochromic device according to another embodiment of the present invention. The same descriptions as those of FIGS. 1 and 2 will not be repeated.

Referring to FIG. 3, the electrochromic device 100 includes a first electrode unit 110, a first coloring material layer 120 disposed on the first electrode unit 110 and including a first coloring material, An electrolyte layer 130 disposed on the material layer 120, a second color fading material layer 140 disposed on the electrolyte layer 130 and including a second color fading material, a second color fading material layer 140 disposed on the second color fading material layer 140, A second terminal unit 160 connected to the second electrode unit 150 and the first electrode unit 110 and connected to the first terminal unit 160 and the second electrode unit 150 having the first polarity, 170).

One of the first electrode unit 110 and the second electrode unit 150, for example, the second electrode unit 150 includes the transparent substrate 152 and the transparent electrode 154 according to an embodiment of the present invention. can do. Here, the transparent electrode 154 is disposed on a surface of the transparent substrate 152 facing the electrolyte layer 130, and may include a transparent conductive material.

The other one of the first electrode unit 110 and the second electrode unit 150, for example, the first electrode unit 110, includes a conductive substrate of a predetermined color. Here, the predetermined color may be a white color, but is not limited thereto, and may have various colors except transparency. The conductive substrate of a predetermined color may be formed by plating or vapor-depositing at least one of Sn, Ag, Al, Cu, Al, and Mo. The conductive substrate of a predetermined color may have a single layer or a multi-layer structure. The predetermined color may vary depending on the type and size of the metal to be plated or deposited.

In this manner, the first electrode 110, a case comprising a conductive substrate having a predetermined color other than a transparent, as well as to more clearly show the color of the letters, numbers, color fading area as a picture or the like, ^10-2 To 10 < ^-3 > OMEGA / sq.

Meanwhile, according to an embodiment of the present invention, the electrolyte layer 130 comprises at least one of a polymerizable monomer, a polymerizable oligomer and a polymer, a first ionic liquid, and a second ionic liquid different from the first ionic liquid . Wherein at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the first ionic liquid, and the second ionic liquid comprises from 10 to 30 wt% of one polymerizable monomer, polymerizable oligomer and polymer, Preferably 10 to 20 wt%, and the first ionic liquid and the second ionic liquid may be contained in an amount of 70 to 90 wt%, preferably 80 to 90 wt%. If the first ionic liquid and the second ionic liquid are contained below such a numerical range, the rate of discoloration may be slowed down. And, if the first ionic liquid and the second ionic liquid are contained in such a range exceeding the numerical value range, the electrolyte layer is separated from the electrode layer, and the electrolyte layers can be coalesced.

Here, the polymerizable monomer, the polymerizable oligomer and the polymer serve as a matrix in the electrolyte layer 130, and may be used as a matrix in the form of an acrylic monomer, an acrylic oligomer, an acrylic polymer, an acrylate monomer, an acrylate oligomer, , A carbonate-based monomer, a carbonate-based oligomer, and a carbonate-based polymer. For example, the polymerizable monomers, polymerizable oligomers and polymers may be selected from the group consisting of urethane acrylates, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, methyl styrene, vinyl ester compounds, vinyl chloride, vinylidene chloride, Acrylamide, tetrafluoroethylene, vinyl acetate, methyl vinyl ketone, ethylene, styrene, paramethoxystyrene, p-cyanostyrene, polyethylene glycol acrylate, etc. These may be used singly or in combination of two or more kinds. The polymerizable monomer, the polymerizable oligomer and the polymer may be monomers, oligomers and polymers exemplified in the following formulas (1) to (3).

The polymerizable monomer, the polymerizable oligomer and the polymer may be polymerizable by UV or heat. To this end, the electrolyte layer 130 may further include an azo compound such as AIBN (Azobisisobutyronitrile), which is a thermal initiator, or Irgacure-184, Darocure, etc., which is a photoinitiator. The thermal initiator or photoinitiator may be contained in an amount of 0.5 to 1.5 wt% of the electrolyte layer 130, and examples of the photoinitiator are shown in the following formula (4).

On the other hand, an ionic liquid means a salt in a liquid state, and it is made of ions, but the cation and the anion are electrically neutral because the charge is made zero. According to an embodiment of the present invention, the first ionic liquid is an ionic liquid of a different kind than the second ionic liquid, and the first ionic liquid is not reactive with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer And the second ionic liquid may be an ionic liquid capable of reacting with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer.

For example, the cation included in the first ionic liquid may include ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium ( pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolium, thiazolium, triazolium (triazolium), and the like, anions include _{^{halogen, BF 4 -, PF 6 -}} , a sulfonate-based _{[(SO 2 R) O]} -, imide _{[(SO 2 R) 2 N} ] -, methide - [(SO ₂ R) ₃ C] ^- , and the like. Where, R may be a halogen, CF _3, C ₂ F _5, and other aryl or alkyl substituents that may be a pair of electrons. For example, the first ionic liquid may include 1-decyl-3-mathylimidazolium bis (trifluoromethanesulfonyl) imide having the structure of Formula 5: imide, but is not limited thereto.

The first ionic liquid can be evenly dispersed in the matrix, as it is not capable of reacting with the matrix, i.e., at least one of the polymerizable monomer, the polymerizable oligomer and the polymer.

In contrast, the second ionic liquid is capable of reacting with the matrix, i.e., at least one of the polymerizable monomer, the polymerizable oligomer and the polymer. Accordingly, in the present specification, the second ionic liquid can be mixed with the reactive ionic liquid. In order for the second ionic liquid to be able to react with the matrix, the second ionic liquid may be an ionic liquid in which the cation has a carbon double bond or a carbon triple bond.

It may be a reactive ionic liquid. Here, the reactive ionic liquid may be an ionic liquid in which the cation has a carbon double bond or a carbon triple bond. When an ionic liquid having a carbon double bond or a carbon triple bond is irradiated with UV, radicals are generated and the generated radical can react with at least one of polymerizable monomers, polymerizable oligomers and polymers added as a matrix . Thus, the second ionic liquid can be cross-linked with the matrix and can maintain stable dispersion in the electrolyte layer.

In this case, the second ionic liquid may include at least one of imidazolium or ammonium, and the cation may further include vinyl or acrylate groups. For example, the second ionic liquid can be prepared by reacting a cation with a cation selected from the group consisting of 1-methyl-3-vinylimidazolium or [3- (methacryloylamino) propyl] trimethylammonium ([ 3-methacryloylamino) propyl] trimethylammonium). For example, the second ionic liquid may have one of the formulas (6), (7) or (8).

When the cation of the second ionic liquid is the same as in Formula 7, the second ionic liquid is 3 - [(methacryloylamino) propyl] trimethylammonium bis (trifluoromethanesulfonyl) imine having the structure of Formula But are not limited to, 3 - [(methacrylamino) propyl) trimethylammonium bis (trifluoromethanesulfonyl) imide].

In this case, the second ionic liquid may be contained in an amount of 5 to 15 parts by weight, preferably 5 to 10 parts by weight, more preferably 5 to 8 parts by weight, based on 10 parts by weight of the first ionic liquid. If the second ionic liquid is contained in a larger amount than this numerical range, the reaction with the matrix occurs excessively, and the entire electrolyte layer may become stiff, thereby increasing the resistance and decreasing the coloring speed. If the second ionic liquid is contained in an amount less than this range, a phenomenon that the electrolyte layer is transferred and diffused toward the electrode portion may occur.

Meanwhile, the electrolyte layer 130 according to an embodiment of the present invention may further include a metal salt, and the metal salt may include lithium ions. The lithium ion may be contained in the form of, for example, the formula (10) and may be contained in an amount of 30 wt% or less, preferably 10 to 30 wt% of the total electrolyte layer (130).

When the electrolyte layer 130 contains lithium ions, it is possible to obtain a fast discoloration rate due to the low vapor pressure of the ionic liquid, non-flammability, electrochemical stability, and high ionic conductivity at room temperature.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Manufacture of electrochromic devices

A 200 nm thick WO ₃ thin film was formed on the ITO transparent electrode by a bar coating method and a 200 nm thick Prussian blue thin film was formed on the other ITO transparent electrode in the same manner. A dam (sealing part) having a thickness of 100 mu m was formed, an electrolyte layer composition was coated on the dam, and then irradiated with 1,100 mJ / cm < ² > in an ultraviolet exposure machine to produce an electrochromic device of 10 cm * 10 cm.

Preparation of electrolyte layer composition

≪ Example 1 >

Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) of 1.03 mol / L was mixed with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the ionic liquid, and the photoinitiator of Formula 4 in a weight ratio of 9: 90: Was added. Wherein at least one of the polymerizable monomer, the polymerizable oligomer and the polymer is a urethane acrylic oligomer and an acrylic monomer mixed in a weight ratio of 1: 1, and the first ionic liquid of the formula (5) and the second ionic liquid of the formula (9) Weight ratio.

≪ Example 2 >

Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) of 1.03 mol / L was mixed with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the ionic liquid, and the photoinitiator of Formula 4 in a weight ratio of 9: 90: Was added. Wherein at least one of the polymerizable monomer, the polymerizable oligomer and the polymer is a urethane acryl oligomer and an acrylic monomer mixed in a weight ratio of 1: 1, and the first ionic liquid of formula (5) and the second ionic liquid of formula (9) To 5 wt%.

≪ Example 3 >

Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) of 1.03 mol / L was mixed with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the ionic liquid, and the photoinitiator of Formula 4 in a weight ratio of 9: 90: Was added. Wherein at least one of the polymerizable monomer, the polymerizable oligomer and the polymer is a urethane acryl oligomer and an acrylic monomer mixed in a weight ratio of 1: 1, and the first ionic liquid of the formula (5) and the second ionic liquid of the formula (9) By weight.

≪ Comparative Example 1 &

Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) of 1.03 mol / L was mixed with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the ionic liquid, and the photoinitiator of Formula 4 in a weight ratio of 9: 90: Was added. Wherein at least one of the polymerizable monomer, the polymerizable oligomer and the polymer is a urethane acrylic oligomer and an acrylic monomer mixed in a weight ratio of 1: 1 and the first ionic liquid of Formula 5 and the second ionic liquid of Formula 9 By weight.

≪ Comparative Example 2 &

Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) of 1.03 mol / L was mixed with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer, the ionic liquid, and the photoinitiator of Formula 4 in a weight ratio of 9: 90: Was added. At this time, at least one of the polymerizable monomer, the polymerizable oligomer and the polymer is a urethane acrylic oligomer mixed with a 1: 1 weight ratio and an acrylic monomer, and only the first ionic liquid of formula (5) is used.

≪ Comparative Example 3 &

1 M LiClO ₄ was dissolved in propylene carbonate.

Charge and discharge tests of the electrochromic devices produced in Examples 1 to 3 and Comparative Examples 1 to 3 were carried out. One cycle was started by starting at the initial 3V voltage, followed by coloring with a voltage of -2V for 60sec, followed by decolorization with a voltage of 2V for 60sec. Then, the transmittance (T%) at the time of coloring and discoloration was measured using a UV-V spectrophotometer analyzer.

Table 1 shows the results of measuring the transmittance and time at the time of coloring and decoloring after driving 10 cycles, and Table 2 shows the results of measuring transmittance and time at the time of coloring and decoloring after driving 2,000 cycles. FIG. 4 is a photograph of the electrolyte layer of Example 3 after repeated driving, and FIG. 5 is a photograph of the electrolyte layer of Comparative Example 1 after repeated driving.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 coloring Transmittance (%) 41 40 39 40 40 41 Time (sec) 15 13 10 9 10 17 decolorization Transmittance (%) 81 81 81 82 82 81 Time (sec) 13 12 9 9 9 15 Discoloration range (ΔT%) 40 41 42 42 42 41 Average discoloration time (sec) 14 12.5 9.5 9 9.5 16

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 coloring Transmittance (%) 48 44 41 Can not drive
(1,900 cycles) Can not drive
(1,500 cycles) Can not drive
(690 cycles) Time (sec) 30 24 20 decolorization Transmittance (%) 75 74 75 Time (sec) 24 21 18 Discoloration range (T%) 27 30 34 Average discoloration time (sec) 27 22.5 19

Referring to Tables 1 to 2, when the first ionic liquid and the second ionic liquid are contained at a weight ratio of 4: 6, 5: 5, and 6: 4 as in Examples 1 to 3, When the second ionic liquid is contained in an amount of 5 to 15 parts by weight with respect to 10 parts by weight of the first liquid, it can be driven even after 2000 cycles.

In particular, referring to Tables 1 to 2, when the first ionic liquid and the second ionic liquid are contained in a weight ratio of 5: 5 and 6: 4 as in Examples 2 to 3, that is, When the second ionic liquid is contained in an amount of 5 to 10 parts by weight based on 10 parts by weight of the composition, the range of discoloration is large and the average discoloration time is shorter than that of Example 1.

In particular, referring to Tables 1 to 2, when the first ionic liquid and the second ionic liquid are contained at a weight ratio of 6: 4 as in Example 3, that is, When the 2-ionic liquid is contained in an amount of 5 to 8 parts by weight, the discoloration range is larger and the average discoloration time is shorter than those of Examples 1 and 2.

4 to 5, when the first ionic liquid and the second ionic liquid are contained at a weight ratio of 6: 4 as in the third embodiment, the ion gel of the electrolyte layer is not destroyed. However, When the second ionic liquid is out of the range of 5 to 15 parts by weight with respect to 10 parts by weight of the first ionic liquid as in Comparative Example 1, the ionic gel is broken and transferred to the ITO transparent electrode side and diffused.

The components of the first ionic liquid and the second ionic liquid contained in the electrolyte layer of the electrochromic device according to the embodiment of the present invention can be analyzed by IR analysis (InfraRed spectroscopy) or NMR (Nuclear Magnetic Resonance) The content can be analyzed by TGA analysis (thermogravimetric analysis).

The electrochromic device and the electrochromic device according to the embodiments of the present invention can be applied to a variety of applications such as a vehicle mirror, a building window, a display device, and an ESL device.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (10)

The first substrate,
A first electrode disposed on the first substrate,
A first color fading material layer disposed on the first electrode and including a first color fading material,
An electrolyte layer disposed on the first color fading material layer,
A second color fading material layer disposed on the electrolyte layer and including a second color fading material,
A second electrode disposed on the second color fading material layer, and
And a second substrate disposed over the second electrode,
Wherein at least one of the first substrate and the second substrate is a transparent substrate and at least one of the first electrode and the second electrode is a transparent electrode,
Wherein the electrolyte layer comprises at least one of a polymerizable monomer, a polymerizable oligomer and a polymer, a first ionic liquid, and a second ionic liquid that is different from the first ionic liquid,
The first ionic liquid is an ionic liquid that is not reactive with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer,
Wherein the second ionic liquid is an ionic liquid capable of reacting with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer. The method according to claim 1,
Wherein the second ionic liquid is an ionic liquid in which the cation is a carbon double bond or a carbon triple bond. 3. The method of claim 2,
Wherein the second ionic liquid is an ionic liquid in which the cation is a vinyl group or an acrylate group. The method of claim 3,
Wherein the second ionic liquid is an ionic liquid in which the cation further comprises at least one of imidazolium or ammonium. 5. The method of claim 4,
The second ionic liquid may be selected so that the cation is selected from the group consisting of 1-methyl-3-vinylimidazolium or [3- (methacryloylamino) propyl] trimethylammonium ([ methacryloylamino) propyl] trimethylammonium). 3. The method of claim 2,
Wherein the first ionic liquid has a cation such that the cation is selected from the group consisting of ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, at least one of pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolium and thiazolium, and triazolium. And an electrochromic device. The method according to claim 6,
Wherein the second ionic liquid is contained in an amount of 5 to 15 parts by weight based on 10 parts by weight of the first ionic liquid. 3. The method of claim 2,
Wherein the electrolyte layer further comprises a lithium salt. 3. The method of claim 2,
Wherein the electrolyte layer further comprises a photoinitiator. A first electrode disposed on the first substrate; a first color-change material layer disposed on the first electrode and including a first color-change material; an electrolyte layer disposed on the first color-change material layer; And a second substrate disposed on the second electrode, wherein the first substrate and the second substrate are disposed on the first substrate and the second substrate, the second color-change material layer including a second color-change material, Wherein at least one of the first and second electrodes is a transparent substrate and at least one of the first electrode and the second electrode is a transparent electrode and the electrolyte layer comprises at least one of a polymerizable monomer, a polymerizable oligomer and a polymer, And a second ionic liquid that is different from the first ionic liquid, wherein the first ionic liquid is reacted with at least one of the polymerizable monomer, the polymerizable oligomer and the polymer And that neunghaji ionic liquid, wherein the second ionic liquid is an ionic liquid in an electrochromic device with at least one possible response of the polymerizable monomers, polymerizable oligomers and polymers,
A first terminal portion connected to the first electrode and having a first polarity,
And a second terminal portion connected to the second electrode and having a second polarity.

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