KR20180031145A - A Electrochromic Device, method for preparing the same, and Method for Controlling Optical Properties of the same - Google Patents

Abstract

The present invention relates to an electrochromic element, a manufacturing method thereof, and an optical characteristics control method thereof. The electrochromic element according to the present invention can comprise an electrochromic layer having two or more kinds of crystalline tungsten oxide (WOx) particles having different numbers of oxygen bonds.

Description

TECHNICAL FIELD [0001] The present invention relates to an electrochromic device, a method of manufacturing the same, and a method of controlling optical characteristics of the device,

The present application relates to an electrochromic device, a method of manufacturing the same, and a method of controlling optical characteristics of the device.

The electrochromic device refers to a reversible color change that occurs when an electrochromic material electrochemically induces an oxidation or reduction reaction, and the device configured to change the optical characteristics of the device using the electrochromic device is referred to as an electrochromic device.

In an electrochromic device, a change in optical characteristics due to electrochromism, for example, a degree of change in transmittance, generally depends on the electrochromic material used. For example, when nickel oxide (NiO _x ) is used as an electrochromic material, the light transmittance of the device becomes low as it becomes dark brown upon coloring. However, in recent years, various fields that utilize the electrochromic phenomenon have been diversified, and therefore, there is a need for a product that can be designed with different optical characteristics depending on the application.

One object of the present invention is to provide an electrochromic device and a method of manufacturing the same.

Another object of the present invention is to provide an electrochromic device in which optical characteristics such as transmittance and contrast ratio can be controlled by actively adjusting the light transmittance to visible light.

It is another object of the present invention to provide a method for controlling the optical characteristics of an electrochromic device.

These and other objects of the present application can be provided by the present application, which is described in detail below.

In one example of this application, the present application relates to an electrochromic device. The electrochromic device of the present application includes two or more kinds of crystalline tungsten oxide particles differing in the number of oxygen bonds, so that the contrast ratio of the device can be actively controlled. More specifically, the present application is based on the finding that when amorphous, that is, when amorphous tungsten oxide is used as an electrochromic material or when one type of tungsten oxide having the same number of oxygen bonds is used, the light transmittance and the contrast ratio ) Can be further increased or decreased to control the electrochromic device to have optical characteristics suitable for various uses.

In the present application, the term "contrast ratio" may mean a value obtained by dividing the light transmittance upon discoloration of the electrochromic device by the light transmittance upon coloring. In the present application, "light transmittance" can mean a light transmittance measured in a wavelength range of 380 nm to 780 nm, more specifically, at a wavelength of 550 nm, unless otherwise specified

The electrochromic device of the present application may include two electrode layers opposed to each other, an electrochromic layer, and an electrolyte layer. The electrode layer may be provided between two electrode layers, and the electrolyte layer may be provided on one side of the electrochromic layer. 1 shows a cross section of an exemplary electrochromic device according to the present application.

In one example, the electrode layer may comprise a transparent conductive oxide, a nanowire, a metal mesh, or an oxide metal oxide (OMO).

In one example, as the transparent conducting oxide is ITO (Indium Tin Oxide), In 2 O 3 (Indium Oxide), IGO (indium galium oxide), FTO (Fluor doped Tin Oxide), (Aluminium doped Zinc Oxide) AZO, (GZO), antimony doped tin oxide (ATO), indium doped zinc oxide (IZO), niobium doped titanium oxide (NTO), zinc oxide (ZnO), or cesium tungsten oxide .

In one example, the nanowire and the metal mesh may be formed of a material such as silver (Ag), copper (Cu), or aluminum (Al), but are not limited thereto.

The electrode layer containing the above-mentioned electrode-forming material may have a thickness in the range of, for example, 1 nm to 400 nm. In this case, the light transmittance of the electrode layer may be 80% to 90%.

The electrochromic layer of the present application can use crystaline tungsten oxide particles as an electrochromic material. More specifically, the electrochromic layer may include two or more crystalline tungsten oxide (WOx) particles having different numbers of oxygen bonds.

In one example, the tungsten oxide particles may have monoclinic or hexagonal crystals.

In one example, the tungsten oxide particles may have a composition represented by the following formula (1). Among the crystalline tungsten oxide particles represented by the following formula (1), by selecting two or more kinds of particles having different oxygen bonding numbers, different optical characteristics of the particles can be combined. Accordingly, when amorphous tungsten oxide is used as an electrochromic material or when one type of tungsten oxide having the same number of oxygen bonds is used, various optical characteristics such as light transmittance and contrast ratio can be realized.

[Chemical Formula 1]

WOx (2.5? X? 3.0)

In one example, the electrochromic device comprises tungsten oxide (WO _x ) selected from a first particle represented by the following formula (2), a second particle represented by the following formula (3), and a third particle represented by the following formula (4) And may include two or more kinds of particles.

(2)

WO _x (2.5? X? 2.7)

(3)

WO _x (2.7 < x &lt; 2.92)

[Chemical Formula 4]

WO _x (2.92 < x &lt; 3.0)

The tungsten oxide particles represented by the general formulas (2) to (4) are particles in which purple, blue, and yeloow particles are individually selected. When two or more kinds of particles are selected and used , And the optical characteristics of the electrochromic device can be changed in various ways.

In one example, the tungsten oxide particles may include two kinds of particles among the first to third particles. For example, 1 to 99 parts by weight of one kind of particles selected from the first to third particles, and 1 to 99 parts by weight of particles having different oxygen-binding-number to the selected one kind of particles, . &Lt; / RTI &gt; For example, the electrochromic layer may comprise 1 to 99 parts by weight of the first particles and 1 to 99 parts by weight of the second particles, or 1 to 99 parts by weight of the second particles and 1 to 99 parts by weight of the third particles. 1 to 99 parts by weight of the first particles, and 1 to 99 parts by weight of the third particles. In the present application, &quot; parts by weight &quot; may mean weight ratios between the respective components. For example, 1 to 99 parts by weight of the first particles and 1 to 99 parts by weight of the second particles means that the weight ratio of the first particles and the second particles is in the range of 1 to 99: 1 to 99 parts by weight . More specifically, the tungsten oxide particles may include 20 to 80 parts by weight of the first or second particles, and 20 to 80 parts by weight of the third particles. However, the tungsten oxide particles are not particularly limited thereto.

In one example, the tungsten oxide particles may include all of the first to third particles. More specifically, the electrochromic layer may contain 1 to 98 parts by weight of the first particles, 1 to 98 parts by weight of the second particles, and 1 to 98 parts by weight of the third particles.

As described above, when two or more kinds of crystalline tungsten oxide particles having different oxygen binding numbers are used, it is possible to provide a device in which optical characteristics are variously changed as compared with the case where one kind of particles is used or amorphous tungsten oxide is used .

Also, as described below, in the case of the electrochromic layer formed by conventional sputtering deposition or the like, the oxygen-coupling number of tungsten oxide can be controlled by controlling the ratio of oxygen to argon during deposition, WO _x is not a crystalline particle type but an amorphous substance and is not a plurality of particles having different oxygen bonding numbers, so that the optical characteristics of the device can not be varied as described herein.

In one example, the shape of the crystalline tungsten oxide particles may be spherical, polyhedron, or rod-shaped. In the case of the spherical shape, it may be used to mean an elliptical spherical shape. In the case of the rod-like shape, it may mean a case where the length ratios in the longitudinal direction and the lateral direction are different, and the shape of the cross section may be circular, elliptical, polygonal or amorphous, and is not particularly limited.

In one example, the spherical tungsten oxide particles may have a diameter of 5 to 50 nm or less. When the diameter is within the above-mentioned range, since the specific surface area of the particles is wide, the number of sites capable of reacting with the insertion of the electrolyte ion is increased, so that the reactivity required for discoloration can be increased. When the particles are elliptical spherical, the long diameter of the elliptical section, that is, the long diameter may have the diameter in the above range.

In one example, the polyhedral or rod-shaped tungsten oxide particles may have a volume of 65,000 nm ³ or less.

In one example, the electrochromic layer has a thickness in the range of 10 nm to 500 nm, and the light transmittance to the wavelength in the visible light region may range from 5% to 90%. More specifically, the electrochromic layer may have a light transmittance of 5% to 20% at the time of coloring and a light transmittance of 80% to 90% at the time of discoloring when the discoloration reaction of the tungsten oxide particles occurs, have.

[General formula]

WO ₃ (transparent at the time of decolorization) + xe ^- + xM + ⇔ M _x WO ₃ (blue in coloring)

(Where M ⁺ can be H ⁺ , or an ion of an alkali metal such as Li ⁺ , Na ⁺ or K ⁺ ).

The change in light transmittance in the above-mentioned range is more preferably in the range of about 20% to about 80%, which is the light transmittance generally observed when particles of WO ₃ are used, on the assumption that the thickness of the electrochromic layer is the same. It means that a wide range of light transmittance can be realized in the electrochromic layer of the present application.

In one example, the electrochromic layer of the present application may have a contrast ratio in the range of 2 to 10. The large contrast ratio means that the transmittance varies greatly in coloring and decoloring, but a small number of contrast ratios may be required if necessary. The present application can provide an electrochromic device having various contrast ratios depending on needs because two or more kinds of crystalline tungsten oxide particles represented by any one of the above formulas (2) to (4) are mixed and used in a specific content range.

The electrolyte layer may mean a layer for providing ions involved in the discoloration reaction. The type of the electrolyte used in the electrolyte layer is not particularly limited, and may be a liquid type, a gel type, or an inorganic solid electrolyte. The inorganic solid electrolyte may comprise LiPON or Ta ₂ O ₅ . In addition, the inorganic solid electrolyte may be one in which components such as B, S, and W are partially added to LiPON or Ta ₂ O ₅ .

In one example, the gel-type electrolyte may comprise one or more compounds, for example, compounds comprising H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ . As a non-limiting example, the electrolyte layer can be LiClO ₄ , LiBF ₄ , or LiPF ₆ Can be used as an electrolyte salt.

In another example, the gel type electrolyte layer may further include a carbonate compound. Since the carbonate compound has a high dielectric constant, the conductivity of the ions provided by the lithium salt can be increased. As the carbonate compound, any one or more of propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC) may be used.

In one example, the electrolyte layer may have a thickness ranging from 30 [mu] m to 200 [mu] m, but is not particularly limited thereto.

In one example, the permeability of the electrolyte layer may range from 80% to 95%.

The electrochromic device may further include an ion storage layer. The ion storage layer may mean a layer capable of balancing the ions involved in the deposition / discoloration reaction of the tungsten oxide particles contained in the electrochromic layer.

In one example, the ion storage layer may be provided on the opposite side of the electrolyte layer surface in contact with the electrochromic layer. In this connection, Fig. 2 shows a cross-section of the electrochromic device according to another example of the present application.

In one example, the ion storage layer may comprise an inorganic oxide having oxidative color development properties. Specifically, an ion storage layer, Cr, Mn, Fe, Co, Ni, Rh, and an oxide or more of any one of metal selected from Ir, that is, LiNiOx, IrO _2, NiO, V ₂ O _5, LixCoO _2, Rh ₂ O ₃ or CrO ₃ may be used, but the present invention is not limited thereto.

The ion storage layer may have a thickness in the range of, for example, 10 nm to 500 nm.

In one example, the light transmittance of the ion storage layer may vary from 20% to 80%. For example, it may have a light transmittance in the range of 20% to 45% in coloring and 55% to 80% in decolorizing.

In one example, the outer surface of the substrate, that is, the opposite surface of the electrode layer and the surface of the electrode layer facing the electrochromic layer, the surface opposite to the surface of the electrode layer facing the electrolyte layer, A transparent substrate may be provided on the opposite surface of the electrode layer surface facing the storage layer. The translucent substrate may refer to a substrate having a transmittance in the range of about 50% to 90%. The type of the light-transmitting substrate is not particularly limited, and for example, transparent glass or polymer resin may be used. More specifically, a polyester film such as PC (Polycarbonate), PEN (poly (ethylene naphthalate)) or PET (poly terephthalate), an acrylic film such as poly (methyl methacrylate) Or a polyolefin film such as PP (polypropylene) may be used, but the present invention is not limited thereto.

In one example, the electrochromic device may further include a power source. The electrical connection between the power source and the electrochromic device or the magnitude of the voltage applied to the electrochromic device by the power supply can be suitably selected by those skilled in the art.

In another example related to the present application, the present application relates to a method of manufacturing an electrochromic device. More specifically, the present invention relates to a method of manufacturing an electrochromic device in which optical characteristics such as a light transmittance and a contrast ratio can be controlled. The manufacturing method may include the step of applying a coating solution containing two or more crystalline tungsten oxide (WOx) particles having different oxygen-bond numbers on the first substrate.

The coating solution may comprise an organic solvent, an additive, and tungsten oxide particles. In one example, the coating solution may comprise 60 to 90 parts by weight of an organic solvent, 0.05 to 15 parts by weight of an additive, and 5 to 30 parts by weight of tungsten oxide particles.

In one example, the organic solvent used in the coating solution may be an aqueous or alcohol-based solvent that can be evaporated through heat treatment after application of the coating solution.

In one example, as the additive used in the coating solution, a known organic or inorganic binder may be used. More specifically, TEOS (tetraethyl orthosilicate) or silane-based compounds may be used.

The specific kind, particle content, shape and other properties of the tungsten oxide particles contained in the coating solution are as mentioned above.

The method of applying the solution on the first substrate is not particularly limited. For example, by spin coating, dip coating, spray coating, gravure coating, flow coating, or bar coating. In this connection, when the deposition method, which is one of the widely used methods for forming the electrochromic layer, is used, only tungsten oxide with an armophous property is provided, so that crystalline tungsten oxide particles can not be realized, Can not be achieved.

The method for manufacturing an electrochromic device may further include a step of coating the coating solution on a base material, followed by heat treatment. Although the heat treatment conditions are not particularly limited, for example, the organic solvent can be evaporated and the heat treatment can be performed at a temperature at which the organic / inorganic binder can be cured. In one example, a heat treatment can be performed in the range of 50 캜 to 350 캜.

As the first substrate to which the coating solution is applied, for example, a known release film, a light-transmitting plastic substrate, a glass substrate, or a conductive substrate containing a transparent conductive oxide such as ITO mentioned above may be used. Also, in some cases, a laminate of the listed materials may be used. For example, the transparent conductive oxide layer can be used as a first substrate by depositing a transparent plastic substrate or a laminate provided on a glass substrate through vapor deposition.

In one example, when the first substrate comprises a first transparent conductive oxide layer, the coating solution may be applied on the first transparent conductive oxide layer, whereby one side of the electrochromic layer formed after the heat treatment And may contact one surface of the first transparent conductive oxide layer. Alternatively, when the stacked body is used as the first substrate, the electrochromic layer may be provided by applying the coating solution on one side of the transparent conductive oxide layer in the stacked body, followed by heat treatment.

In one example, the method may include the step of providing an electrolyte layer and a second substrate on an opposite surface of the electrochromic layer provided with the transparent conductive oxide layer. The constitution and other properties of the electrolyte layer are as mentioned above. Also, the second substrate may include a transparent conductive oxide layer like the first substrate. In this case, the transparent conductive oxide layer included in the second substrate may be referred to as a second transparent conductive oxide layer.

The manner of providing the electrolyte layer and the second substrate in the electrochromic layer is not particularly limited. For example, when the electrolyte layer includes a liquid electrolyte, an electrolyte layer may be formed while a liquid electrolyte is injected between the first and second substrates. When the electrolyte layer includes a gel-type electrolyte, The substrates and the electrolyte layer can be bonded together. In the case of an inorganic solid electrolyte, an electrolyte layer may be provided on one surface of the first and second substrates through deposition or the like, and then the remaining electrolyte may be bonded to the remaining substrate. In this manner, one surface of the second transparent conductive oxide layer may be in contact with one surface of the electrolyte layer.

In one example, the second substrate may comprise a second transparent conductive oxide layer and an ion storage layer. In this case, the ion storage layer may be provided on one side of the second transparent conductive oxide layer by a deposition method such as sputtering or vacuum deposition, or by the above-mentioned known coating method. The second substrate having the above-described structure can also be bonded to the first substrate via the electrolyte layer through the above-mentioned method. Specifically, the opposite surface of the surface of the ion storage layer, which is in contact with one surface of the second transparent conductive oxide layer, may be configured to contact the electrolyte layer. 2 schematically shows a cross-section of an electrochromic device according to an exemplary embodiment of the present application including an ion storage layer. The structure and other characteristics of the ion storage layer are as described above.

In another example of this application, the present application relates to a method of controlling the optical characteristics of an electrochromic device. The configuration and other characteristics of the electrochromic device are the same as those described above.

The control method includes controlling the optical characteristics of the electrochromic device by configuring the electrochromic layer so as to include two or more kinds of crystalline tungsten oxide (WOx) particles differing in color-changing material, that is, can do.

In one example, the optical characteristic may be a light transmittance or a contrast ratio, and the optical characteristic may vary according to a content ratio between the two or more kinds of crystalline tungsten oxide particles.

The present application has the effect of providing an electrochromic device capable of actively controlling the optical characteristics of the electrochromic device.

Fig. 1 schematically shows a cross-section of an exemplary electrochromic device according to an example of the present application. The electrochromic device 100 may include electrode layers 140 and 110, a electrochromic layer 120, and an electrolyte layer 130.
Fig. 2 schematically shows a cross-section of an exemplary electrochromic device according to another example of the present application. The electrochromic device 100 may include electrode layers 140 and 110, an electrochromic layer 120, an electrolyte layer 130, and an ion storage layer 120 '.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the scope of protection of the present invention is not limited by the following embodiments.

Example  One

75 parts by weight of tungsten oxide (WO ₃ ) particles having a diameter of about 20 nm and 25 parts by weight of tungsten oxide (WO _2.90 ) particles having a diameter of about 20 nm with 2 wt% of a dispersant (TEOS) To prepare a coating solution. The coating solution was coated on a PET / ITO substrate through spin coating and then heat-treated to prepare an electrochromic layer having a thickness of 230 nm. A sample was prepared by bonding one surface of the electrochromic layer to another PET / ITO substrate, immersing the sample in a liquid electrolyte (1 M LiClO ₄ in PC), measuring optical characteristics for a wavelength of 550 nm, Are shown in Table 1.

Example  2

The optical characteristics were measured in the same manner as in Example 1 except that the content of the tungsten oxide particles and the thickness of the electrochromic layer were different.

Example  3

The optical characteristics were measured in the same manner as in Example 1 except that the content of the tungsten oxide particles and the thickness of the electrochromic layer were different.

Reference example  One

The optical characteristics were measured in the same manner as in Example 1 except that the content of the tungsten oxide particles and the thickness of the electrochromic layer were different.

Reference example  2

The optical characteristics were measured in the same manner as in Example 1 except that the content of the tungsten oxide particles and the thickness of the electrochromic layer were different.

[Table 1]

As shown in Reference Example 1, when only WO ₃ particles were used, the light transmittance difference (ΔT) at the time of attaching and detaching was high at a thickness of 200 nm to 300 nm, but the contrast ratio was low. In addition, as in Reference Example 2, when only WO _2.90 particles are used, it is confirmed that the difference in light transmittance (DELTA T) during attachment and detachment is low, but the contrast ratio is high.

On the other hand, in Examples 1 to 3 in which contents of concurrent tungsten oxide particles are different from each other, the light transmittance difference? T becomes smaller and the contrast ratio increases as the content of WO ₃ decreases Show. This means that by using two or more kinds of crystalline titanium oxide having different oxygen numbers as in the present invention, various optical characteristics such as a difference in light transmittance and a contrast ratio can be realized.

100: electrochromic device
140, 110: electrode layer
120: electrochromic layer
130: electrolyte layer
120 ': ion storage layer

Claims (38)

Two electrode layers facing each other;
An electrochromic layer provided between the two electrode layers and including two or more kinds of crystalline tungsten oxide (WO _x ) particles having different numbers of oxygen bonds; And
An electrolyte layer provided on one surface of the electrochromic layer;
And an electrochromic device.
The electrochromic device according to claim 1, wherein the tungsten oxide (WO _x ) particles have a monoclinic crystal or a hexagonal crystal.
The method of claim 1, wherein the tungsten oxide (WO _x) particles electrochromic device is selected from tungsten oxide (WO _x) particles represented by the following general formula (1).
[Chemical Formula 1]
WOx (2.5? X? 3.0)
2. The electrochemical device according to claim 1, wherein the tungsten oxide (WO _x ) particles are selected from the group consisting of a first particle represented by the following formula (2), a second particle represented by the following formula (3) Discoloration element:
(2)
WO _x (2.5? X? 2.7)
(3)
WO _x (2.7 < x < 2.92)
[Chemical Formula 4]
WO _x (2.92 &lt; x &lt; 3.0)
5. The electrochromic device according to claim 4, wherein 1 to 99 parts by weight of one kind of particles selected from the first to third particles, and 1 to 99 parts by weight of particles having different oxygen- .
5. The electrochromic device according to claim 4, comprising 1 to 98 parts by weight of the first particles, 1 to 98 parts by weight of the second particles, and 1 to 98 parts by weight of the third particles.
The electrochromic device according to claim 1, wherein the tungsten oxide particles (WO _x ) are selected from spherical, polyhedral, and rod-shaped particles.
The electrochromic device according to claim 7, wherein the tungsten oxide particles (WO _x ) are spherical particles having a diameter of 50 nm or less.
The electrochromic device according to claim 7, wherein the tungsten oxide particles (WO _x ) are polyhedral particles or rod-shaped particles having a volume of 65,000 nm ³ or less.
The electrochromic device according to claim 1, wherein the electrochromic layer has a thickness in the range of 10 nm to 500 nm and has a light transmittance to a wavelength in a visible light range of 5% to 90%.
The electrochromic device according to claim 1, wherein a contrast ratio of the electrochromic layer is in a range of 2 to 10.
The electrochromic device according to claim 1, wherein the electrolyte layer comprises a gel type electrolyte, an inorganic solid electrolyte or a liquid type electrolyte.
The electrochromic device according to claim 12, wherein the electrolyte layer has a thickness in the range of 30 탆 to 200 탆 and a light transmittance to a wavelength in a visible light region is 80% to 95%.
The method of claim 1, wherein the electrode is the electrode is ITO (Indium Tin Oxide), In 2 O 3 (indium oxide :), IGO (indium galium oxide), FTO (Fluor doped Tin Oxide), Aluminium doped Zinc Oxide (AZO) (GZO), antimony doped tin oxide (ATO), indium doped zinc oxide (IZO), niobium doped titanium oxide (NTO), zinc oxide (ZnO), cesium tungsten oxide (CTO) / Metal / Oxide).
The electrochromic device according to claim 16, wherein the transparent electrode has a thickness in the range of 1 nm to 400 nm and has a transmittance of 80% to 90% with respect to a wavelength in a visible light region.
The ion storage device according to claim 1, further comprising an ion storage layer provided on a surface opposite to the surface of the electrolyte layer in contact with the electrochromic layer, wherein the ion storage layer comprises at least one of Cr, Mn, Fe, Co, Ni, And at least one oxide selected from the metals selected.
17. The electrochromic device according to claim 16, wherein the ion storage layer has a thickness in the range of 10 nm to 500 nm and has a light transmittance to a wavelength in a visible light range of 20% to 80%.
The electrochromic device according to claim 1, further comprising a light-transmitting substrate on each of outer surfaces of the two electrode layers.
Applying a coating solution containing two or more kinds of crystalline tungsten oxide (WOx) particles having different oxygen-bond numbers on a first substrate, and then performing heat treatment to prepare an electrochromic layer;
Wherein the electrochromic device further comprises an electrochromic device.
20. The method of claim 19, wherein application of the coating solution comprises:
Wherein the electrochromic device is formed by spin coating, dip coating, spray coating, gravure coating, flow coating or bar coating.
20. The method of claim 19, wherein the tungsten oxide (WOx) particles have a monoclinic crystal or a hexagonal crystal.
The method of manufacturing an electrochromic device according to claim 19, wherein the tungsten oxide (WOx) particles are selected from tungsten oxide (WOx) particles represented by the following formula (1).
[Chemical Formula 1]
WOx (2.5? X? 3.0)
The method of claim 19, wherein the tungsten oxide (WO _x ) particles are selected from the group consisting of a first particle represented by the following formula (2), a second particle represented by the following formula (3), and a third particle represented by the following formula A method of manufacturing a discoloration element.
(2)
WO _x (2.5? X? 2.7)
(3)
WO _x (2.7 < x < 2.92)
[Chemical Formula 4]
WO _x (2.92 &lt; x &lt; 3.0)
The electrochromic device according to claim 19, comprising 1 to 99 parts by weight of one kind of particles selected from the first to third particles, and 1 to 99 parts by weight of particles having different oxygen-bonding numbers with the selected one kind of particles &Lt; / RTI &gt;
The electrochromic device according to claim 19, wherein 1 to 98 parts by weight of the first particles, 1 to 98 parts by weight of the second particles, and 1 to 98 parts by weight of the third particles are contained.
The method of manufacturing an electrochromic device according to claim 19, wherein the tungsten oxide particles (WO _x ) are selected from spherical, polyhedral, and rod-shaped particles.
20. The method of claim 19, wherein the first substrate comprises a first transparent conductive oxide layer, and the electrochromic layer is provided on one surface of the first transparent conductive oxide layer.
28. The method of manufacturing an electrochromic device according to claim 27, further comprising the step of providing an electrolyte layer and a second substrate on a surface opposite to the surface of the electrochromic layer in contact with the first transparent conductive oxide layer.
29. The method of claim 28, wherein the second substrate comprises a second transparent conductive oxide layer, and one surface of the second transparent conductive oxide layer is in contact with one surface of the electrolyte layer.
The electrochemical device according to claim 28, wherein the second substrate comprises a second transparent conductive oxide layer and an ion storage layer, wherein the electrochromic layer is provided on an opposite surface of the ion storage layer, / RTI &gt;
Two electrode layers facing each other; An electrochromic layer provided between the two electrodes; And an electrolyte layer provided on one side of the electrochromic layer, wherein the method comprises the steps of:
A method for controlling an optical characteristic of an electrochromic device comprising the electrochromic layer so as to include two or more kinds of crystalline tungsten oxide (WO _x ) particles having different numbers of oxygen bonds.
32. The method of claim 31, wherein the tungsten oxide (WO _x ) particles have a monoclinic crystal or a hexagonal crystal.
32. The method of claim 31, wherein the optical characteristic control method of an electrochromic device wherein the tungsten oxide (WO _x) the particles are selected from the following tungsten oxide (WO _x) particles represented by the following formula (1).
[Chemical Formula 1]
WOx (2.5? X? 3.0)
The method of claim 31, wherein the tungsten oxide (WO _x ) particles are selected from the group consisting of a first particle represented by the following formula (2), a second particle represented by the following formula (3), and a third particle represented by the following formula A method for controlling optical characteristics of a color changing element.
(2)
WO _x (2.5? X? 2.7)
(3)
WO _x (2.7 < x < 2.92)
[Chemical Formula 4]
WO _x (2.92 &lt; x &lt; 3.0)
35. The electrochromic device according to claim 34, wherein 1 to 99 parts by weight of one kind of particles selected from the first to third particles and 1 to 99 parts by weight of particles having different oxygen bonding numbers with the selected one kind of particles / RTI &gt;
35. The method of claim 34, wherein the first particle comprises 1 to 98 parts by weight of the first particle, 1 to 98 parts by weight of the second particle, and 1 to 98 parts by weight of the third particle.
32. The method according to claim 31, wherein the tungsten oxide particles (WO _x ) are selected from spherical, polyhedral, and rod-shaped particles.
32. The method according to claim 31, wherein the optical characteristic is a transmittance or a contrast ratio, and the optical characteristic varies according to a content ratio between two or more kinds of crystalline tungsten oxide particles.

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