KR101657965B1 - Electrochromic device, electrode structure therefor, and manufacturing method thereof - Google Patents

Electrochromic device, electrode structure therefor, and manufacturing method thereof Download PDF

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KR101657965B1
KR101657965B1 KR1020160028036A KR20160028036A KR101657965B1 KR 101657965 B1 KR101657965 B1 KR 101657965B1 KR 1020160028036 A KR1020160028036 A KR 1020160028036A KR 20160028036 A KR20160028036 A KR 20160028036A KR 101657965 B1 KR101657965 B1 KR 101657965B1
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South Korea
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electrode
layer
electrochromic
bus electrode
bus
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KR1020160028036A
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Korean (ko)
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곽준영
정영희
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애드크로 주식회사
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

An electrochromic device manufactured by a method of forming a bus electrode on an electrochromic layer is disclosed. A bus electrode is formed directly on the electrochromic layer using a printing process. In the case of a small-area device, main bus electrodes are formed at corner portions of the first electrode portion and the second electrode portion, respectively. In addition, in the case of a large area device, a bus electrode array is disposed in the central portion of the electrochromic layer in addition to the corner portion, and an insulating film is formed on the surface of the bus electrode array to prevent direct contact between the electrolyte layer and the bus electrode. A bus bar and an insulating layer are formed on an electrochromic layer to provide an electrochromic device having little influence on a uniform color change rate and a small area response rate in a large area electrochromic device as well as a small area.

Description

ELECTROCHROMIC DEVICE, ELECTRODE STRUCTURE THEREFOR, AND MANUFACTURING METHOD THEREOF FIELD OF THE INVENTION The present invention relates to an electrochromic device,

The present invention relates to a field of an electrochromic device, and more particularly, to a field of electrochromic device, which can form a bus electrode on an electrochromic layer and can be mass-produced by a simple manufacturing process, and can exhibit uniform and fast electrochromic characteristics An electrode structure for the electrochromic device, and a method of manufacturing the same.

The electrochromic device utilizes a phenomenon in which an electrochromic material due to an externally applied voltage reversibly changes color due to an oxidation-reduction reaction. Such electrochromic devices can not only provide visibility, but also have various applications such as a smart window, an automobile room mirror, a notebook, a mobile phone, and a decorative design since users can actively control the transmittance.

The electrochromic device typically comprises a first electrode of transparent electrical conductivity, a second electrode disposed opposite to the first electrode, a second electrode disposed between the first electrode and the second electrode on the first and second electrodes, An electrochromic layer formed on the first electrode, and an electrolyte disposed between the first electrode and the second electrode. The transparent electroconductive electrode is mainly made of plastics or glass substrates coated with indium doped tin oxide (ITO) or fluorine doped tin oxide (FTO). The electrochromic materials that can be used to form the electrochromic layer can be divided into an oxidative coloring type in which the color is changed by the oxidation reaction and a reducing coloring type in which the color is changed by the reduction reaction. Examples of the reducing coloring materials include inorganic metal oxides such as WO 3 , TiO 2 and Nb 2 O 5, and organic high molecular substances such as polyaniline, polythiophene polybiorgen, and polypyrrole. Examples of the oxidative coloring substance include prussian blue PB), IrO 2 , NiO, and the like.

One of the most important parts in the performance evaluation of the electrochromic device is the uniform discoloration rate and the discoloration time. Such an electrochromic property depends on the method of forming the electrochromic layer. In addition, when the area of the electrochromic layer is increased, the rate of discoloration near both extreme ends applying the applied voltage due to the resistance of the transparent conductive layer is the fastest, It can not have a uniform discoloration rate. Further, in order to commercialize the electrochromic device, it is necessary to maintain a uniform coloring speed and an appropriate response time irrespective of the area. In order to solve this problem in the prior art, there have been proposed a method of lowering the sheet resistance of the transparent electrode, a method of improving the conductivity of the electrochromic layer, and a method of implementing the same characteristics as the small- . However, these conventional methods have technical limitations that can not be overcome.

First, in the method of lowering the sheet resistance of the transparent electrode, the height of the visible light transmittance by controlling the thickness and the refractive index when forming the transparent electrode is a method of applying a multilayer thin film structure (oxide / metal / oxide structure) of the metal oxide / 10-0939842), a method of reducing sheet resistance by inserting a metal line of a few micrometers level in a transparent electrode (Korean Patent Laid-Open No. 10-2008-0122062), and a method of using a transparent electrode using silver nano wire (AgNWs) 1319443) have been tried, but all of these methods are not only durable due to the electrochemical stability of the metal, and even if the durability problem is solved, due to the IR drop caused by the fabrication of a large area electrochromic device Area dependence is inevitable and can not be a fundamental alternative.

A method of improving the conductivity of the electrochromic layer (Korean Patent Laid-open Publication No. 10-2015-0076780 and Korean Patent Laid-open Publication No. 10-2013-0066755) is also incapable of avoiding area dependence due to voltage drop.

It is believed that the only way to avoid area dependence in the prior art is to make large-area electrochromic devices into small device arrangements, as shown in Fig. Since the elements to be formed are the same as those of the small-area elements, the driving characteristics of the large-area elements are determined by the spacing of the bus bar patterns of the small-area elements constituting the array unit.

Conventionally, an attempt has been made to arrange such a small area element array structure, but the structure is such that the bus bar 2 directly contacts the transparent electrode 3 on the transparent electrode as shown in Fig. As can be seen from Fig. 12, such a conventional electrochromic device requires that the electrochromic layer 1 also be patterned into small unit cells. The electrochromic layer 1 is patterned by forming an electrochromic layer 1 on the whole area and then patterning through etching (Korean Patent Laid-Open No. 10-2008-0051280, Korean Patent Registration No. 10-0936121) , Patterning using masking during deposition, and the like, all have a disadvantage in that the process is complicated and the cost is increased. Even if the electrochromic layer 1 is difficult to pattern, the bus bar 2 is ideally patterned in a narrow gap between the electrochromic layers 1 and the insulating layer 6 for preventing contact with the electrolyte 7 can be accurately It is not easy to pattern at the position, and it is difficult to solve the problem because the manufacturing cost increases and the manufacturing difficulty is added.

Korean Patent No. 10-1175607

DISCLOSURE Technical Problem The present invention has been devised to solve the problems of the prior art, and it is an object of the present invention to provide a method of forming a bus electrode on an electrochromic layer or an ion storage layer, not a method of directly contacting a bus electrode with a transparent conductive electrode, The present invention provides an electrochromic device having the same electrochromic rate and discoloration time in a small area as well as in a large area.

The present invention provides a method of manufacturing an electrochromic device including the above-described improved electrochromic layer.

The present invention also provides an electrode structure applied to the above-described improved electrochromic device.

The present invention provides an electrode structure for an electrochromic device, comprising: a conductive layer; A electrochromic layer disposed on the conductive layer; A bus electrode having a pattern for exposing the electrochromic layer on the electrochromic layer; And an insulating film formed on a surface of the bus electrode.

The bus electrode may have the same or similar pattern repeated on the electrochromic layer. The bus electrode may be a stripe pattern or a lattice pattern.

The insulating layer may expose an end of the bus electrode for external connection of the bus electrode.

The present invention also provides an electrochromic device comprising: an electrolyte layer; And at least one of the first electrode portion and the second electrode portion includes an electrochromic layer, a first electrode portion and a second electrode portion disposed on both sides of the electrolyte layer, A bus electrode having a pattern exposing the electrochromic layer and an insulating layer formed on a surface of the bus electrode, wherein the insulating layer shields the contact between the bus electrode and the electrolyte layer.

The insulating layer may expose an end of the bus electrode for external connection of the bus electrode.

The first electrode part may include an oxidation coloring type electrochromic layer, and the second electrode may include a reducing coloring type electrochromic layer.

The first electrode portion may include an electrochromic layer, and the second electrode portion may include an ion storage layer.

The bus electrode may be any one selected from the group consisting of Ir, Ag, Cu, Au, Cr, Al, W, Zn, Ni, Fe, Pt, Pb, and their alloys, carbon black, , Carbon nanotubes (Carbon Nanotube), and combinations thereof.

The bus electrode may be a striped or lattice pattern.

The insulating film may be one of a polymer and an inorganic material, or a mixture thereof, or an organic or inorganic hybrid.

The present invention also provides a method of manufacturing an electrochromic device, comprising: (a) forming a first electrode portion and a second electrode portion, respectively; And (b) laminating the first electrode portion and the second electrode portion via an electrolyte layer, wherein at least one of the first electrode portion and the second electrode portion includes an electrochromic layer, A bus electrode having a pattern exposing the electrochromic layer on the layer, and an insulating layer formed on a surface of the bus electrode to block contact between the bus electrode and the electrolyte layer.

The electrochromic layer contacts the electrolyte layer by an exposure pattern of the bus electrode and the insulating film.

(A-1) forming a bus electrode having a pattern exposing the electrochromic layer on the electrochromic layer; and forming at least one of the first electrode unit and the second electrode unit. And (a-2) forming an insulating film on the surface of the bus electrode.

The bus electrode may be formed using one of screen printing, photolithography, imprinting, and inkjet printing.

The line width and thickness of the pattern of the bus electrode may be 1 to 500 mu m.

The thickness of the insulating film may be 2 to 1000 mu m.

The bus electrode may be striped or latticed.

The present invention also provides an electrochromic device comprising: an electrolyte layer; And a first electrode portion and a second electrode portion laminated on both sides of the electrolyte layer, respectively, wherein the first electrode portion and the second electrode portion include a conductive layer, an electrochromic layer formed on the conductive layer, And a main bus electrode formed on the electrochromic layer, wherein the main bus electrodes of the first and second electrode portions are in non-contact with the electrolyte layer.

The present invention also provides a method of manufacturing an electrochromic device, comprising: forming a first electrode array plate having a plurality of first electrode units arranged and a second electrode unit array plate having a plurality of second electrode units arranged; Laminating the first electrode unit array plate and the second electrode sub-plate array through an electrolyte layer array; And cutting the laminated structure into a plurality of individual elements, wherein the first electrode unit array plate and the second electrode unit array plate each have a conductive layer, an electrochromic layer formed on the conductive layer, And a main bus electrode formed in an array on the color change layer.

The main bus electrodes of the first and second electrode unit array plates are not in contact with the electrolyte layer of the electrolyte layer array.

According to the present invention, as the area of the transparent electrode on which the electrochromic layer is raised is increased, the electrical resistance of the transparent electrode does not have a uniform color change speed and the response speed also sharply decreases. , A large-area electrochromic device can be realized by using a structure having an arrayed effect of small devices. The electrochromic device of the present invention can have an effect of arranging substantially a plurality of small elements by arranging the bus electrodes in a pattern in which the electrochromic layer is patterned on the electrochromic layer and exposed to the electrochromic layer. Such a structure of the present invention can provide an electrochromic device having the same electrochromic rate and discoloration time in a small area as well as in a large area. This structure of the present invention can also be realized without patterning the electrochromic layer. Further, such a structure can be applied to electrochromic layers formed by various methods such as electrochemical deposition, chemical bath deposition, sol-gel method and sputtering, and they can all have the same electrochromic effect. Therefore, it is possible to vary the size of the device according to the demand of the purchaser, and it is possible to provide an electrochromic device having a uniform coloring speed and a fast response speed in a large area electrochromic device as well as a small area. In addition, since the bus bar and the wiring line for the bus electrode formed on the electrochromic layer and the insulating film formed thereon are simple in their formation process and excellent in film stability and durability, the production cost can be lowered and various kinds It is very easy to manufacture a large-area electrochromic device of the present invention. Such an electrochromic device of the present invention can be mass-produced in a very simple manner in both cases of a small area and a large area.

1A is a perspective view illustrating an electrochromic device according to a preferred embodiment of the present invention.
1B and 1C are cross-sectional views of an electrochromic device according to a preferred embodiment of the present invention shown in FIG. 1A.
FIGS. 2A and 2B are views illustrating a process of fabricating a first electrode unit and a second electrode unit, respectively, employed in the electrochromic device according to the preferred embodiment of the present invention.
3 is a view illustrating a process of manufacturing an electrochromic device according to a preferred embodiment of the present invention.
4 is a view showing an electrochromic device according to a preferred embodiment of the present invention, and is a view for explaining formation of a main bus bar.
5 is a cross-sectional view illustrating an electrochromic device according to another embodiment of the present invention.
6 to 11 are views illustrating a method of manufacturing an electrochromic device according to another embodiment of the present invention.
12 is a cross-sectional view schematically showing a conventional electrochromic device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the embodiments of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

Briefly, the present invention is a method for forming a bus electrode on an electrochromic layer, which can be mass-produced in a simple manner in a large area as well as a small area, without patterning the electrochromic layer, Provided is an electrochromic device in which a discoloring effect is ensured. Such an electrochromic device includes a bus electrode having a uniform pattern formed on the electrochromic layer. In the case of the small area device, only the main bus electrode disposed near the edge of the electrochromic layer is formed. In the case of the large area, bus electrodes having a uniform pattern on the electrochromic layer in addition to the main bus electrode disposed in the vicinity of the edge A wiring line is disposed and an insulating film is formed thereon. The insulating film formed on the surface of the bus electrode or the wiring line blocks the contact between the bus electrode and the wiring line and the electrolyte layer.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

1A to 1C are views showing an electrochromic device according to a preferred embodiment of the present invention. 1A is a perspective view of the electrochromic device of the present invention, FIG. 1B is a cross-sectional view taken along line A-A 'of FIG. 1A, and FIG. 1C is a cross-sectional view taken along line B-B' of FIG. 1A.

1A to 1C, an electrochromic device according to a preferred embodiment of the present invention includes an electrolyte layer 30, a first electrode portion 10 laminated on both sides (upper and lower portions in the drawing) of the electrolyte layer 30, And a second electrode unit 20.

The first electrode unit 10 and the second electrode unit 20 are formed of the electrochromic layers 11 and 21, the bus electrodes 12 and 22 disposed on the electrochromic layers 11 and 21, 12, and 22, respectively.

The electrochromic layers 11 and 21 of the electrochromic device according to the preferred embodiment of the present invention can be formed on the substrates 14 and 24 and the conductive layers 13 and 23 formed on the substrates 14 and 24 . Here, the substrates 14 and 24 may be flexible plastic or glass, and the conductive layers 13 and 23 may be transparent. The electrochromic layers 11 and 21 can be coated on the conductive layers 13 and 23 by using a coating method such as a wet coating method. When a plastic substrate is used as the substrates 14 and 24, plastic such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polycarbonate (PC) Any substrate can be used. The transparent conductive layers 13 and 23 may be formed of indium doped tin oxide (ITO) and fluorine doped tin oxide (FTO). The electrical resistance may range from 5 to 100 Ω / sq. The better.

The electrochromic layers 11 and 21 are formed using a silicon-based binder sol coating solution in which nanoparticles such as prussian blue (PB), which is an oxidative discoloring substance, or tungsten oxide (WO 3 ) . Examples of the reducing coloring materials applicable to the present invention include inorganic metal oxides such as WO 3 , TiO 2 and Nb 2 O 5 , and organic high molecular substances such as polyaniline, polythiophene polybioorgan, polypyrrole, Type materials include Prussian blue (PB), IrO 2 , NiO, and the like.

Bus electrodes 12 and 22 employed in the present invention are formed on the electrochromic layers 11 and 21. These bus electrodes 12 and 22 have a pattern that exposes the electrochromic layers 11 and 21. The bus electrodes 12 and 22 can expose the upper surface of the electrochromic layers 11 and 21 by having a pattern such as a stripe, a cross stripe or the like. Preferably, the bus electrodes 12 and 22 may have a structure in which a uniform pattern is repeated.

In the illustrated example, the bus electrodes 12 and 22 have a stripe pattern, which may be referred to as a bus bar pattern.

By forming a pattern such as a stripe bus bar or a lattice pattern wiring line that exposes the electrochromic layers 11 and 21 on the electrochromic layers 11 and 21 as described above, the electron transfer rate due to the oxidation- Even if a large-sized device is fabricated, it is possible to drive a device which not only has a uniform discoloration rate but also shows little change in response speed with respect to a small area.

The insulating films 15 and 25 are formed on the surfaces of the bus electrodes 12 and 22 so that the bus electrodes 12 and 22 are not exposed to the electrolyte layer 30. Therefore, the insulating films 15 and 25 are disposed on the upper (upper surface) side and the side (side surface) of the bus bar or wiring line of the bus electrodes 12 and 22, respectively.

As described above, the insulating films 15 and 25 are formed on the surfaces of the bus electrodes 12 and 22 (upper surface and side surface) of the respective bus bars in the illustrated example, thereby forming the electrochromic layers 11 and 21 in the electrolyte layer 30 The bus electrodes 12 and 22 are shielded from being exposed to the electrolyte layer 30.

1A to 1C, the first electrode unit 10 and the second electrode unit 20 are disposed on both sides of the electrolyte layer 30 such as an electrolyte solution or a polymer electrolyte to constitute an electrochromic device . When electricity is applied to the electrochromic device according to the preferred embodiment of the present invention, coloration and discoloration are achieved by an oxidation-reduction reaction.

Another example of an electrochromic device of the present invention may be one comprising a first electrode unit 10, and the second electrode portion 20 includes the electrochromic layer 11, an ion storage layer.

In the electrochromic device of the present invention, an insulating film may not be formed at least on the upper surface portion of the end portions of the bus electrodes 12 and 22. [ The main bus bars 16 and 26 are disposed at this portion. As described below, the first electrode unit 10 and the second electrode unit 20 can be laminated so that the first electrode unit 10 and the second electrode unit 20 are shifted from each other with respect to the electrolyte layer 30. Thus, an end portion of the bus electrode on which the insulating film is not formed is exposed to the outside, and the main bus bars 16 and 26 are disposed in the exposed portion. Such a configuration makes it possible to easily and quickly manufacture the electrochromic device of the present invention by a printing process or the like.

Hereinafter, a method of manufacturing an electrochromic device according to a preferred embodiment of the present invention will be described in detail with reference to FIGS. 2A, 2B, 3 and 4.

First, the first electrode unit 10 and the second electrode unit 20 are manufactured, and then laminated on both sides of the prepared electrolyte layer 30. For example, it can be realized by disposing the electrolyte layer 30 on the first electrode portion 10 and disposing the second electrode portion 20 on the electrolyte layer 30.

The first electrode portion 10 or the second electrode portion 20 forms the conductive layers 13 and 23 on the substrates 14 and 24. Thereafter, electrochromic layers 11 and 21 are formed on the conductive layers 13 and 23, respectively.

Here, the electrochromic layer 11 of the first electrode unit 10 may be formed of an oxidative colored electrochromic layer, and the second electrode unit 20 may be formed of a reduced coloring electrochromic layer.

In the electrochromic device according to another embodiment of the present invention, the first electrode unit 10 may include an electrochromic layer 11 and the second electrode unit 20 may include an ion storage layer.

When an oxidative coloring type electrochromic layer is applied to the electrochromic layer 11 of the first electrode unit 10, an oxidative coloring type such as prussian blue (PB) can be used. When an electrochromic layer is applied to the electrochromic layer 21 of the second electrode unit 20, for example, a reducing coloring type such as tungsten oxide (WO 3 ) can be used.

For reference, the coating liquid for forming the electrochromic layers 11 and 21 of the present invention can be prepared by various known techniques.

Next, bus electrodes 12 and 22 are formed on the electrochromic layers 11 and 21 as shown on the right side in Figs. 2A and 2B. The bus electrodes 12 and 22 are formed to have a stripe pattern or a lattice pattern so as to expose a part of the electrochromic layers 11 and 21. The bus electrodes 12 and 22 may be formed using a patterning method such as screen printing, photolithography, imprinting, and inkjet printing.

For example, the bus electrodes 12 and 22 formed on the electrochromic layers 11 and 21 can be formed by patterning with a screen printing ink containing silver (Ag) using a sprin printing method. As in the illustrated example, the line width and thickness of the bus electrodes 12 and 22 are preferably as thin as possible. Here, the line width of the bus electrodes 12 and 22 refers to the line width of the bus bar in the case of the stripe pattern and the line width of the wiring line in the case of the lattice pattern in which the lattice pattern is formed.

If the line width of the bus electrodes 12 and 22 is large, the pattern may become invisible to be used as a window or a mirror. If the bus electrodes 12 and 22 have a large film thickness, The distance of movement of the electrons by the oxidation-reduction reaction becomes longer, which causes the rate of discoloration to be slowed down. The line width and thickness of the bus electrode are preferably in the range of 1 to 500 mu m.

The conductive ink used for the bus electrodes 12 and 22 should be used within a range that does not cause deformation of the base material when dried. When using a plastic base material, the conductive ink should have a high conductivity even after heat treatment at 150 ° C or less. In general, silver (Ag) is used as a conductive filler, but Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Tc, Ru, , At least one metal such as Cd, In, Sn, Sb, W, Os, Ir, Pt, Ag, Pb and the like or an alloy or alloy oxide thereof, carbon black, graphite, Carbon nanotubes) and conductive inks capable of being cured at a low temperature or UV curable, such as hybrid inks containing any one or more components selected from the group consisting of conductive carbon and conductive polymer.

Next, as shown in the left side of Figs. 2A and 2B, insulating films 15 and 25 are formed on the surfaces of the bus electrodes 12 and 22, respectively.

The insulating films 15 and 25 may be formed by coating an insulating film such as a polyimide film or a polyester film on the bus electrodes 12 and 22 or an insulating film such as an acrylic film, a silicon film, a polyethylene terephthalate film, , Polyester, and the like can be formed by screen printing. In addition, it can be formed by a screen printing method using a thermosetting ink which causes thermal curing in infrared rays and ultraviolet rays. The polymer used for the insulating films 15 and 25 should be free from chemical reaction with the electrolyte after drying. If the formed bus electrodes 12 and 22 are stable without chemical reaction with the electrolyte used in the device, the insulating films 15 and 25 can be omitted.

Since the main bus bars 16 and 26 must be connected to the end portions of the bus electrodes 12 and 22, the portions are exposed. The insulating films 15 and 25 may be formed on the entire surface of the bus electrodes 12 and 22 except for the corresponding portions, and then the insulating films 15 and 25 may be removed.

Thereafter, as shown in FIG. 3, the electrolyte layer 30 is interposed between the first electrode unit 10 and the second electrode unit 20 to perform laminating. This can be realized by applying the electrolyte layer 30 on the first electrode unit 10 and then disposing the second electrode unit 20 on the electrolyte layer.

For example, when a gel electrolyte containing a lithium salt is applied on the first electrode unit 10, portions where the bus electrodes are exposed are excluded. The main electrodes 16 and 26 are disposed at the end portions where the bus electrodes 12 and 22 are exposed, as will be described in detail below.

The electrolyte used can be liquid, gel, or solid. When using a liquid electrolyte, a sealant is used to prevent leakage. The thickness of the device can be minimized by causing the first and second electrodes to face each other with respect to the electrolyte layer formed when the two types of electrodes are laminated in a sandwich type.

4 is a view showing an electrochromic device according to a preferred embodiment of the present invention, and is a view for explaining formation of a main bus bar. In the right side of FIG. 4, other elements are omitted for the sake of understanding.

The pattern shapes and intervals of the bus electrodes 12 and 22 may vary depending on the shape and area of the device. In the case of a small area, it is possible to have the same discoloration rate in the same whole area by only a stripe pattern, but in the case of a rectangular or asymmetric type device, Effect can be obtained. In addition, the pattern interval of the bus electrodes 12 and 22 is influenced by the thickness of the electrochromic layers 11 and 21, the thickness of the electrolyte layer 30, and the thickness of the pattern, and thus an optimization process is required.

Hereinafter, Comparative Examples and Examples will be described in detail.

≪ Comparative Examples 1 and 2 >

PB and WO 3 nano electrochromic thin films having areas of 3 × 3 cm 2 (Comparative Example 1) and 100 × 100 cm 2 (Comparative Example 2) were prepared by the method of Patent Document 10-1175607.

≪ Examples 1 and 2 >

After the nano electrochromic layers 11 and 21 were prepared in the same manner as in Comparative Example 2, the patterned screen frame was formed on the electrochromic layers 11 and 21 by using a screen printing method, and a silver paste solution And then heat-treated at 130 ° C. for 30 minutes to form bus electrodes 12 and 22 on the electrochromic layers 11 and 21. The bus bar spacing of the stripe pattern was 3 cm (Example 1) and the bus bar spacing of the cross stripe pattern pattern was 6 cm (Example 2), and the line width was about 500 μm.

The insulating films 15 and 25 are formed by adhering a polyimide film after leaving a portion where the main bus bars 16 and 26 are connected to the bus electrodes 12 and 22.

The polymer electrolyte layer 30 is formed on the first electrode part 10 which is the PB electrode having the insulating films 15 and 25 and the second electrode part 20 which is the WO 3 electrode is sandwich type And then laminated. At this time, the patterns of the two electrodes were shifted.

Main bus bars 16 and 26 were attached to exposed portions of the bus electrodes 12 and 22, and a voltage was applied to these portions to confirm the electrochromic characteristics. Comparative Example 1 was applied at ± 2 V for 20 seconds, Comparative Example 2 was applied at ± 2 V for 30 minutes, and Examples 1 and 2 were applied at ± 2 V for 30 seconds.

Table 1 below shows the electrochromic characteristics of the electrochromic device prepared in Comparative Examples 1 and 2 and Examples 1 and 2 according to the present invention. In Comparative Examples 1 and 2, the response time was within a few seconds when the device area was 3 × 3 cm 2, but the response time was increased by more than 20 minutes at 100 × 100 cm 2, and the discoloration rate in the device was not constant. However, as shown in Examples 1 and 2, even when the area of the device was increased to 100 x 100 cm 2, the response time did not increase significantly.

As shown in Table 1, by introducing the bus electrode pattern into the electrochromic layer, it was possible not only to reduce the response time in coloring and decoloring, but also to increase the color contrast ratio.

Element area
(㎠) Electrochromic device patterning When coloring Decolorization pattern interval Response time Transmittance
(%) Response time Transmittance
(%) Comparative Example 1 3 x 3 - - - 6.0 seconds 15 7 seconds 70 Comparative Example 2 100 x 100 - - - 20 minutes> 15 25 minutes> 70 Example 1 100 x 100 stripe

Figure 112016022636875-pat00001
3cm 5 seconds 15 6 seconds 71 Example 2 100 x 100 Plaid
Figure 112016022636875-pat00002
 6cm 4 seconds 15 4 seconds 71

Hereinafter, an example of applying the electrochromic device fabrication method of the present invention to a device having a small area will be described.

5 is a cross-sectional view schematically showing an electrochromic device according to another embodiment of the present invention.

The electrochromic device according to another embodiment of the present invention can be applied to mass production of small area devices in an easy manner. In the electrochromic device according to this another example, the first electrode portion 10 and the second electrode portion 20 are arranged so as to be shifted with respect to the electrolyte layer 30, and the electrochromic layers 11 and 21 are formed on the edge portions, As shown in FIG. First and second main bus electrodes 16 and 26 are disposed on the edge portions of the exposed electrochromic layers 11 and 21, respectively.

The configuration of this other example of the present invention is similar to that of the large area device of the present invention in that the bus electrode does not directly contact the conductive layers 13 and 23 but contacts the electrochromic layers 11 and 21 in the conductive layer / . In the present invention, the main bus electrodes 16 and 26 are disposed on the electrochromic layers 11 and 21 to form the electrochromic layers 11 and 21 and the electrochromic layers 11 and 21, Respectively. In the case of a small area, there is no difference in electric power supply capability even with such a structure, and instead, it is possible to mass-produce quickly by using a roll-to-roll printing process. In FIG. 5, reference numerals 14 and 24 denote the respective substrates.

Hereinafter, a method of manufacturing an electrochromic device according to another embodiment of the present invention will be described with reference to FIGS.

First, as shown in FIGS. 6A and 6B and FIG. 7A, a first electrode unit array plate 100 in which a plurality of first electrode units are arranged and a second electrode unit 100 in which a plurality of second electrode units are arranged Electrode array plate 200 are formed. For reference, the first and second conductive layers 130 and 230 formed on the first and second substrates 140 and 240 and the first and second substrates 140 and 240, respectively, .

6A and 6B, first and second substrates 140 and 240, such as PET, are formed on the first and second substrates 140 and 240 to form first and second electrode array plates, respectively. The first and second electrochromic layers 110 and 210 are coated on the lower structures having the second conductive layers 130 and 230, respectively, using, for example, a doctor blade method. Here, if the oxidizing-type electrochromic layer 110 is formed on the first electrode unit 100, a reduced-type electrochromic layer 210 may be formed on the second electrode unit 200.

Next, on the first and second electrochromic layers 110 and 210 of the first electrode array plate 100 and the second electrode array plate 200 as shown in FIGS. 7A and 7B, Thereby forming arrays 160 and 260 of the first and second main bus electrodes 16 and 26, respectively. The first and second main bus electrodes 16 and 26 are connected to the first electrode unit 10 and the second electrode unit 20 of the individual disconnection device, Corresponds to the corner portion of the second housing 26. The first main bus electrodes 16 of the first electrode unit array plate 100 and the second main bus electrodes 26 of the second electrode unit array plate 200 are arranged in the center of the electrolyte layer 30, As shown in Fig.

8, a plurality of electrolyte layers 30 are formed on the first or second electrochromic layers 110 and 210 of the first electrode array plate 100 or the second electrode array plate 200, Thereby forming the arrayed electrolyte layer array 300. The formation of the electrolyte layer array 300 prints and coating the electrolyte layers 30 corresponding to the adjacent positions of the first or second main bus electrodes 26 as shown in the figure.

Then, as shown in FIG. 9, the first electrode unit array plate 100 and the second electrode unit array plate 200 are laminated. At this time, in the individual elements, the electrolyte layer 30 formed on the first or second electrode portion is formed on the inner side of the first and second main bus electrodes 16 and 26 of the first and second electrode portions 10 and 20 So that the first main bus electrode 16 of the first electrode unit 10 and the second main bus electrode 26 of the second electrode unit 20 are positioned at the center of each electrolyte layer 30, They are placed in opposite positions.

Next, as shown in Fig. 10, the laminated structure is cut into discrete elements. After cutting, it will be like the plan view and the sectional view shown on the right side.

Subsequently, as shown in FIG. 11, the edge portions on the opposite sides of the first and second main bus electrodes 16 and 26 are removed from the first and second electrode portions 10 and 20 of the cut individual elements. This portion removes a portion corresponding to the outside of the electrolyte layer 30, and can be omitted if the two electrodes are processed so as not to contact each other. For example, if an insulating layer is formed on the first and second main bus electrodes 16 and 26, the contact of the two electrodes can be avoided.

As described above, it is possible to mass-produce electrochromic devices of small area easily by applying the printing method.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.

Claims (21)

1. An electrode structure for an electrochromic device which is laminated to each other with an electrolyte layer sandwiched therebetween, comprising:
Conductive layer;
A electrochromic layer disposed on the conductive layer;
A bus electrode arranged on the electrochromic layer and having a pattern exposing the electrochromic layer;
An insulating layer formed on a surface of the bus electrode, the insulating layer being formed on a surface of the bus electrode to surround the bus electrode and shield the contact with the electrolyte layer, and exposing an end of the bus electrode for external connection of the bus electrode; And
And a main bus electrode arranged to be connected to the exposed end of the bus electrode.
The method according to claim 1,
Wherein the bus electrode is repeated in the same or similar pattern on the electrochromic layer.
The method according to claim 1,
Wherein the bus electrode is a stripe wiring line pattern or a lattice pattern wiring line pattern.
delete As the electrochromic device:
An electrolyte layer; And
And a first electrode portion and a second electrode portion disposed on both sides of the electrolyte layer,
Wherein at least one of the first electrode portion and the second electrode portion includes an electroconductive layer, an electrochromic layer disposed on the electroconductive layer, and an electrochromic layer disposed on the electrochromic layer, An insulating layer formed on a surface of the bus electrode and including an upper surface and a side surface of the bus electrode to shield the bus electrode from the electrolyte layer and expose an end of the bus electrode for external connection of the bus electrode; And a main bus electrode arranged to connect to an exposed end of the bus electrode,
Wherein the first electrode portion and the second electrode portion are laminated so as to be shifted from each other in opposite directions so that the end portion of the bus electrode where the insulating film is not formed is exposed to the outside and the main bus bar is disposed at an end portion of the exposed bus electrode. , An electrochromic device.
delete The method of claim 5,
Wherein the first electrode portion includes an oxidation coloring type electrochromic layer, and the second electrode includes a reducing coloring type electrochromic layer.
The method of claim 5,
Wherein the first electrode portion includes an electrochromic layer, and the second electrode portion includes an ion storage layer.
The method of claim 5,
The bus electrode may be any one selected from the group consisting of Ir, Ag, Cu, Au, Cr, Al, W, Zn, Ni, Fe, Pt, Pb, and their alloys, carbon black, , A carbon nanotube (Carbon Nanotube), and a composite thereof.
The method of claim 5,
Wherein the bus electrode is a stripe wiring line pattern or a lattice pattern wiring line pattern.
The method of claim 5,
Wherein the insulating film is one of a polymer and an inorganic material, or a mixture thereof, or an organic / inorganic hybrid.
A method for producing an electrochromic device, comprising:
(a) forming a first electrode portion and a second electrode portion, respectively; And
(b) laminating the first electrode portion and the second electrode portion so as to be shifted from each other with the electrolyte layer interposed therebetween,
Wherein forming at least one of the first electrode portion and the second electrode portion comprises:
(a-1) forming an electrochromic layer on the conductive layer;
(a-2) forming a bus electrode arranged on the electrochromic layer so as to have a pattern exposing the electrochromic layer; And
(a-3) an insulating film disposed on a surface of the bus electrode to expose an end of the bus electrode for external connection of the bus electrode and to cover the top and side surfaces of the bus electrode so as to prevent contact between the bus electrode and the electrolyte layer; And forming the electrochromic device.
The method of claim 12,
Wherein the electrochromic layer is in contact with the electrolyte layer by an exposure pattern of the bus electrode and the insulating film.
delete The method of claim 12,
Wherein the bus electrode is formed using one of screen printing, imprinting, and inkjet printing.
The method of claim 12,
Wherein a line width and a thickness of the pattern of the bus electrode are 1 to 500 mu m and a thickness of the insulating film is 2 to 1000 mu m.
The method of claim 12,
Further comprising disposing a main bus electrode to be connected to an end of the exposed bus electrode after laminating in step (b).
The method of claim 12,
Wherein the bus electrode is a stripe wiring line or a lattice pattern wiring line.
As the electrochromic device:
An electrolyte layer; And
And a first electrode portion and a second electrode portion laminated on both sides of the center of the electrolyte layer,
Wherein the first electrode portion includes a first conductive layer, a first electrochromic layer formed on the first conductive layer, and a first main bus electrode formed on the first electrochromic layer,
Wherein the second electrode portion includes a second conductive layer, a second electrochromic layer formed on the second conductive layer, and a second main bus electrode formed on the second electrochromic layer,
Wherein the first and second main bus electrodes of the first and second electrode portions are disposed at positions opposite to each other with respect to the electrolyte layer.
A method for producing an electrochromic device, comprising:
Forming a first electrode array plate in which a plurality of first electrode units are arranged and a second electrode unit array plate in which a plurality of second electrode units are arranged;
Laminating the first electrode unit array plate and the second electrode unit array plate through an electrolyte layer array; And
Cutting the laminated structure into a plurality of discrete elements,
Wherein the first electrode unit array plate includes a first conductive layer, a first electrochromic layer formed on the first conductive layer, and a first main bus electrode formed on the first electrochromic layer in an array,
Wherein the second electrode unit array plate includes a second conductive layer, a second electrochromic layer formed on the second conductive layer, and a second main bus electrode formed on the second electrochromic layer in an array. A method for manufacturing an electrochromic device.
The method of claim 20,
Wherein the first and second main bus electrodes of the first and second electrode unit array plates are disposed at positions opposite to each other with respect to a corresponding electrolyte layer of the electrolyte layer array.
KR1020160028036A 2015-12-11 2016-03-09 Electrochromic device, electrode structure therefor, and manufacturing method thereof KR101657965B1 (en)

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