KR20140062640A - Electrochromic and method thereof - Google Patents

Abstract

The present invention relates to an electrochromic device and a manufacturing method thereof and, more particularly, to an electcrochromic device and a manufacturing method thereof, having a fast response property by improving conductivity using a mesh type transparent electrode which includes FTO and/or ITO to control light transmittance by changing the color of an electrochromic material if an electric field is applied.

Description

ELECTROCHROMIC AND METHOD THEREOF [0002]

The present invention relates to an electrochromic device and a method of manufacturing the same. More particularly, the present invention relates to an electrochromic device using a mesh-type transparent electrode including FTO and / or ITO to change the color of the electrochromic material when the electric field is applied, And a method for manufacturing the electrochromic device.

Generally, electrochromic devices are devices used as automobile room mirrors, side mirrors, outer walls or windows of buildings, and curtain substitute glass between rooms and rooms. As the current flows, oxidation and reduction reaction proceeds and the color of the electrochromic material Is manufactured using the principle of changing.

Such a conventional electrochromic device is composed of a transparent electrode layer and a discolored layer electrolyte layer, and in the case of an electrolyte, it is generally constituted by a liquid electrolyte, which is disclosed in a conventional patent application No. 2005-0134753. The electrochromic device disclosed in the above-mentioned conventional patent application No. 2005-0134753 is as shown in Fig.

1 is a side cross-sectional view showing a conventional electrochromic device.

1, a conventional electrochromic device includes first and second substrates 8 and 1 which have a space and are bonded to each other, and an electrolyte layer (not shown) formed between the first substrate 8 and the second substrate 1, (3).

A thin film transistor including a semiconductor layer 5, a gate electrode GE, a source electrode SE and a drain electrode DE is formed on the first substrate 8, (DE) is connected to the first electrode (7). The electrochromic layer 7 is formed on the first electrode 7 so as to be electrically connected to the first electrode 7.

A second electrode 2 is formed on the second substrate 1 and an ion storage layer is formed on the second electrode 2 so as to be electrically connected to the second electrode 2. A plurality of white reflectors are formed on the ion storage layer.

Here, the white reflector reflects the incident light to improve the reproducibility of white.

The electrochromic layer 7 is a material whose transparency is changed by a voltage applied to the first electrode 7 and the second electrode 2. Such an electrochromic device has a red electrochromic layer A green electrochromic layer 7 representing a green gradation, and a blue electrochromic layer 7 representing a blue gradation.

The electrolyte layer (3) serves to conduct ions according to the change of the voltage, and the ion storage layer functions to store the ions.

On the other hand, the drawing number GI not shown represents a gate insulating film for electrically separating the gate electrode GE from the source / drain electrodes SE, DE, and figure 4 represents a protective film for protecting the thin film transistor. No. 6 shows an ohmic contact layer for reducing the contact resistance between the source electrode SE and the semiconductor layer 5 and the contact resistance between the drain electrode DE and the semiconductor layer 5. [

Here, the electrochromic layer may be made of tungsten oxide, nickel oxide, vanadium oxide, which are inorganic electrochromic materials, or alternatively polyaniline, polythiophene, polypyrrole, and viologin derivatives, which are organic electrochromic materials.

The dual inorganic electrochromic materials have advantages over the organic ones in terms of stability and durability. The electrochromic device using the inorganic electrochromic material as described above is disclosed in 'Electrochromic device using a solid inorganic electrolyte protective film and method for manufacturing the same' of Patent Application No. 2006-0077199.

However, the inorganic electrochromic materials included in the above-mentioned conventional documents have a higher resistance than the organic electrochromic materials due to the resistance of the transparent electrode layer (FTO, ITO) and the self-resistance of the electrochromic material and the diffusion of metal ions into the electrochromic material layer There is a disadvantage in that the electrochromic material has a disadvantage in that the electrochromic material has a disadvantage in that the electrochromic material is expensive and the electrochromic material is expensive.

It is an object of the present invention to provide a transparent electrode layer having improved conductivity by printing a transparent electrode layer in a mesh form, And to provide an electrochromic device capable of applying both an inorganic electrochromic material and an organic electrochromic material, and a method of manufacturing the same.

Another object of the present invention is to provide an electrochromic device and a method of manufacturing the electrochromic device, which can improve the electrochromic rate by improving the conductivity by printing the transparent electrode layer with the conductive ink so as to have the mesh shape with the conductive ink through the printing method.

The present invention includes the following embodiments in order to achieve the above object.

A first embodiment of the present invention is an electrochromic device having a color changing by an electrical signal, the electrochromic device comprising: a lower electrode formed on one surface between an upper electrode and a lower substrate formed on one surface of an upper substrate; An electrolyte layer formed of any one of a liquid, a solid, and a UV electrolyte that transmits an electric signal applied from the upper electrode and the lower electrode; And an electrochromic material whose color is changed by an electrical signal applied from the electrolyte, wherein the electrochromic material is mixed with the electrolyte in the electrolyte layer and formed between the upper electrode and the lower electrode.

In the second embodiment of the present invention, at least one of the upper electrode and the lower electrode may be a mesh-type mesh printed on one surface of the upper substrate or the lower substrate by conductive ink by gravure, ) Pattern.

In the third embodiment of the present invention, one of the upper electrode and the lower electrode is formed of a tin oxide conductive film substrate (FTO).

In a fourth embodiment of the present invention, the electrochromic material in the electrolyte layer is selected from the group consisting of 5,10-dihydro-5-methylphenazine and 4-vinylbenzyl chloride 4-vinylbenzyl chloride) in a weight ratio of 1: 1, 5,10-dihydro-5-methylphenazine and methacryloyl- (4,4'-bipyridine) and methacryloyl chloride (1: 1) are mixed in a weight ratio of 1: 1, and a third compound Or more.

In the fifth embodiment of the present invention, the electrochromic material is at least one selected from the group consisting of the first to third compounds and lithium perchlorate.

In a sixth embodiment of the present invention, the electrolyte is a mixture of tetramethylene sulfone, propylene carbonate, and ethylene carbonate in a ratio of 30: 40: 30 (v: v: v) By weight.

In the seventh embodiment of the present invention, the upper substrate and the lower substrate are any one selected from glass, plastic, indium oxide and tin oxide substrates having a sheet resistance of 3 to 9? / ?.

An eighth embodiment of the present invention provides an ink jet printing method, including: an upper electrode printing step of printing an upper electrode by conductive ink on one surface of an upper substrate; An electrolyte printing step of printing an electrolyte on one surface of the upper electrode; And a lower electrode bonding step of bonding the lower electrode printed with the conductive ink after the electrolyte printing step to the upper electrode on which the electrolyte is printed, wherein in the upper electrode printing step and the lower electrode bonding step, And the lower electrode is formed in a mesh pattern having a lattice structure by the conductive ink.

In the ninth embodiment of the present invention, an upper electrode printing step of printing an upper electrode on a glass, an ITO, an FTO, and a plastic substrate with a conductive ink so as to have a mesh-like pattern having a grid structure; A lower electrode bonding step of bonding a lower electrode printed in a mesh pattern having a lattice structure to the upper electrode in a lower substrate formed of any one of glass, ITO, FTO and plastic substrate with the conductive ink after the upper electrode printing step; step; And injecting a liquid or UV electrolyte between the upper electrode and the lower electrode after the lower electrode bonding step and curing the electrolyte.

In the tenth embodiment of the present invention, the upper electrode and the lower electrode are of a mesh type having a lattice structure, and have a line width of 1 to 20 mu m and a line spacing of 100 to 1000 mu m.

In an eleventh embodiment of the present invention, the electrochromic material is 5,10-dihydro-5-methylphenazine and 4-vinylbenzyl chloride. ) And a mixture of 5,10-dihydro-5-methylphenazine and methacryloyl chloride in a weight ratio of 1: : 1, a third compound in which 4,4'bipyridine and methacryloyl chloride are mixed in a weight ratio of 1: 1, and a third compound in which 4,4'-bipyridine and methacryloyl chloride are mixed in a weight ratio of 1: and lithium perchlorate.

In the twelfth embodiment of the present invention, in the lower electrode bonding step, the electrolyte may be laminated at a predetermined height at one side of each of the upper and lower electrodes opposite to each other to adhere and bond the upper and lower electrodes, And is injected into an empty space that is formed as it is sealed.

As described above, when the electrode layer of the electrochromic device is formed into a mesh shape as described above, the electric conductivity can be improved and the electrochromic rate can be improved, so that both the inorganic and organic coloring materials can be applied.

In addition, the present invention can improve the electrical conductivity and the electrochromic rate by forming the mesh-type electrode by the printing method, and the reflectance of the light before and after the electrochromism is greatly reduced, When applied to interior and exterior walls, windows, and interior decorations of the room, there is an effect that the eyes are not fatigued due to reflections of the surrounding people.

1 is a cross-sectional view showing a conventional electrochromic device,
2 is a cross-sectional view illustrating an electrochromic device according to the present invention,
3 is a flowchart showing a first embodiment in a method of manufacturing an electrochromic device according to the present invention,
4 is a flowchart showing a second embodiment of the method for manufacturing an electrochromic device according to the present invention,
5 and 6 are photographs showing a mesh-type transparent electrode in the electrochromic device according to the present invention,
7 is a photograph showing a transparent electrode using a transparent glass in the electrochromic device according to the present invention,
8 is a photograph showing an example of using the electrochromic device according to the present invention.

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

2 is a cross-sectional view illustrating an electrochromic device according to the present invention.

Referring to FIG. 1, the electrochromic device according to the present invention includes an upper substrate 10 and a lower substrate 60, which are made of a light-transmitting material, and an upper electrode 10, which is printed on one surface of the upper substrate 10, A lower substrate 60 printed on one surface of the Hebei substrate and electrically connected to the electric signal and an electrochromic material 40 disposed between the upper substrate 10 and the lower substrate 60, And an electrolyte layer 30 made of a conductive electrolyte for conducting the electrolyte.

The upper electrode 20 and the lower electrode 50 are printed with a conductive ink on the upper surface of the upper substrate 10 and the lower substrate 60 by a printing method such as gravure or offset, Layer 30 as shown in FIG. The upper electrode 20 and the lower electrode 50 may be printed to have a mesh shape using conductive ink or a transparent glass such as an indium oxide (ITO) substrate or a tin oxide conductive film (FTO) substrate . The mesh type transparent electrodes printed by the double conductive ink are as shown in FIGS. 5 and 6, and the transparent electrodes made of the transparent glass such as ITO and FTO are as shown in FIG.

The electrolyte layer 30 is made of a conductive electrolyte so as to transmit an electric signal that is conducted in the upper electrode 20 and the lower electrode 50. The electrolyte layer 30 preferably includes any one of solid, The material 40 is mixed.

That is, it is preferable that the electrolyte is formed on one surface of the upper electrode 20 and the lower electrode 50 by mixing the electrolyte and the electrochromic material 40. In addition, the present invention is produced by printing the solid, liquid, and UV electrolyte on the upper surface of the upper electrode 20 by an offset method and a gravure printing method.

The electrochromic material 40 is oxidized (or reduced) to a size corresponding to the concentration of ions flowing in accordance with a change in voltage in the electrolyte, and changes in color as the transparency is changed. The electrochromic material 40 is synthesized by the following reaction formulas 1 to 3 And at least one of the first to third compounds and lithium perchlorate are selectively applied.

The first to third compounds are as described in the following Reaction Schemes 1 to 3.

[Reaction Scheme 1]

The first compound is prepared according to Reaction Scheme 1 above. More specifically, the first compound is a mixture of 5,10-dihydro-5-methylphenazine and 4-vinylbenzyl chloride in the same ratio , Dissolved in acetonitrile and refluxed for 24 hours to obtain a solution, which was then synthesized by distillation under reduced pressure.

[Reaction Scheme 2]

The second compound was prepared by mixing 5,10-dihydro-5-methylphenazine and methacryloyl chloride in the same ratio and dissolving in acetonitrile The solution was refluxed for 24 hours to obtain a solution, which was synthesized by distillation under reduced pressure.

[Reaction Scheme 3]

The third compound was prepared by mixing 4,4'bipyridine and methacryloyl chloride in the same ratio and dissolving in acetonitrile, refluxing for 24 hours to obtain a solution, It was synthesized by distillation.

Since the synthesis of the first to third compounds is generally well known, the mixing, reflux and reduced pressure distillation processes are omitted.

The electrolyte layer 30 may include an electrochromic material 40 including at least one of the above-described first to third compounds and lithium perchlorate, tetramethylene sulfone, propylene carbonate and ethylene carbonate in a ratio of 30: 40: 30 (v: v: v).

That is, the electrochromic device according to the present invention includes an upper electrode 20 and a lower electrode 50 printed as conductive ink between the upper substrate 10 and the lower substrate 60 by a printing method such as offset and gravure, And an electrolyte layer (30) printed with any one selected from liquid, solid and UV electrolytes was formed.

In this case, since the mesh type transparent electrode printed by the conductive ink is formed in the upper electrode 20 and the lower electrode 50, the electrolyte layer 30 is formed in the upper electrode 20 and the lower electrode 50, The concentration of ions transferred from the electrolyte to the electrochromic material 40 can be increased in a short time, and the rate of discoloration of the electrochromic layer can be greatly improved.

Hereinafter, a method of manufacturing an electrochromic device including the above-described structure will be described in detail with reference to the flowcharts of FIGS. 3 and 4.

3 is a flow chart showing the first embodiment in the method of manufacturing an electrochromic device according to the present invention.

Referring to FIG. 3, the method of manufacturing an electrochromic device according to the first embodiment of the present invention is an embodiment of manufacturing an electrochromic device using a solid electrolyte, and the detailed procedure is as follows.

The first embodiment of the present invention includes a conductive ink manufacturing step S11 for producing a conductive ink, an upper electrode printing step S12 for printing the upper electrode 20 by conductive ink, An electrolyte printing step (S13) of printing an electrolyte on one side, and a lower electrode bonding step (S14) of bonding a lower electrode (50) printed with conductive ink.

The conductive ink manufacturing step S11 may be performed using a conductive material such as silver, copper, gold, chromium, aluminum, tungsten, zinc, nickel, At least one metal powder selected from the group consisting of Ni, Fe, Pt, Pd and Pb and a first non-aqueous solvent having a vapor pressure of not more than 3 torr at 25 캜, A non-aqueous solvent containing a second non-aqueous solvent having a vapor pressure exceeding 3 torr and an organic phosphoric acid compound. The conductive metal powder preferably has an average particle diameter of 1 to 100 nm.

The first non-aqueous solvent may be at least one selected from the group consisting of an alcohol solvent, a glycol solvent, a polyol solvent, a glycol ether solvent, a glycol ether ester solvent, a ketone solvent, a hydrocarbon solvent, a lactate solvent, A side-chain solvent, and a nitrile-based solvent.

The second non-aqueous solvent may be an alcohol solvent, a glycol ether solvent, a glycol ether ester solvent, a ketone solvent, a hydrocarbon solvent, a lactate solvent, an ester solvent, an aprotic sulfoxide solvent and a nitrile solvent And at least one selected from the group consisting of

The organic phosphoric acid compound is preferably an organic phosphoric acid ester.

The conductive ink described above has been described as an example of an ink having conductivity, and other than the above-described configuration, it is possible to replace the ink having conductivity capable of forming a transparent electrode by a printing method as in the case of the present invention.

In the upper electrode printing step S12, a pattern is formed on one surface of the upper substrate 10 by a printing method such as gravure, screen, offset and ink jet using the conductive ink manufactured in the conductive ink manufacturing step S11 The upper electrode 20 is printed. Here, the upper electrode 20 is a mesh type having a lattice structure, and is printed so as to have a mesh shape having a line width of 1 to 20 mu m and a line spacing of 100 to 1000 mu m.

Since the electrochromic device including the mesh electrode of the present invention has a reflectance before color change of 70% to 85% and a reflectance after color change of 5% to 15%, there is almost no fatigue of human eyes due to reflection of light .

However, when the line width of the mesh-shaped electrode is 20 mu m or more, or when the line spacing is 1 to 100 mu m or 1000 mu m or more, the electrochromic device has a reflectance before and after the color change of 90% or more and 60%.

Such a difference can be appreciably confirmed when the electrochromic device is applied to a room mirror of an automobile, for example.

When the line width of the conventional electrochromic device is out of the range of 1 to 20 탆 and the line interval is out of the range of 100 to 1000 탆, the decrease in the reflectance before and after the discoloration is small, I could feel the snow.

However, since the line width and the line spacing are limited as described above, the present invention can measure the reflectance before and after the discoloration at 70 to 85% and 5 to 15%, respectively, so that the driver can not feel the reflection due to the light at all during the night driving, I was able to help with driving.

The upper substrate 10 and the lower substrate 60 may be formed of any one of indium tin oxide (ITO), tin oxide transparent conductive film (FTO), glass and plastic substrates, and a substrate having a sheet resistance of 3 to 9? .

In addition, the lower electrode 50 is printed on one surface of the lower substrate 60 by a printing method such as gravure, screen, offset, and ink jet, and energizes the electric signal in the same manner as the upper electrode 20. The upper electrode 20 and the lower electrode 50 are formed of a transparent electrode capable of transmitting light.

The electrolyte printing step S13 may include printing the solid electrolyte on one side of the upper electrode 20 after the printing of the upper electrode 20 as any one of inkjet, gravure, offset, And printing is performed on one surface to form the electrolyte layer 30. In the first embodiment of the present invention, since the solid electrolyte is printed on the upper electrode 20 by printing, when the glass tube containing the liquid electrolyte is broken due to an external impact such as a liquid electrolyte, the electrolyte can be prevented from flowing down Can be useful.

In the lower electrode bonding step S14, a mesh type pattern is formed on the lower substrate 60 by the conductive ink by any one of offset, gravure, ink jet, and screen printing methods after the electrolyte printing step S13. An electrode is printed, and the printed lower electrode 50 is bonded on one side of the electrolyte layer.

A second embodiment of the present invention is to manufacture an electrochromic device by applying a liquid and / or a UV electrolyte, and will be described in detail with reference to FIG.

4 is a flowchart showing a second embodiment of the method for manufacturing an electrochromic device according to the present invention. The second embodiment is a method for producing an electrochromic device using a liquid electrolyte or a UV electrolyte.

Referring to FIG. 4, a second embodiment of the present invention is a method of manufacturing a conductive ink, comprising the steps of: preparing a conductive ink S21; and performing a conductive ink on the glass, ITO, FTO, A lower electrode bonding step S23 for bonding the lower electrode 50 completed after the upper electrode printing step S22 to the upper electrode printing step S22 for printing the upper electrode 20 in a mesh form, 20) and an upper electrode (50), and an electrolyte injection step (S24) for injecting an electrolyte between the lower electrode (20) and the lower electrode (50).

The conductive ink manufacturing step S21 is a step of manufacturing the ink using the conductive metal powder.

The upper electrode printing step S22 may be performed by printing an upper electrode 20 having a mesh shape on one surface of an upper substrate 10 made of any one of glass, plastic substrate and FTO substrate by an offset, gravure, .

The lower electrode bonding step S23 is a step P for joining the lower electrode 50 to the upper electrode 20. The lower electrode 50 is printed on the one surface of the lower substrate 60 made of any one of glass, plastic, and FTO in the form of a mesh with conductive ink by any one of offset, gravure, screen, and inkjet printing. The upper electrode 20 and the lower electrode 50 are disposed on opposite sides of one side of the lower electrode 50 facing each other so as to form an empty space for injecting a liquid electrolyte or a UV electrolyte between the upper electrodes 20. [ A bonding agent such as silicone and a sealing agent are stacked at a predetermined height and then bonded. Therefore, an empty space for injecting the liquid electrolyte or the UV electrolyte is formed between the upper electrode and the lower electrode.

In the electrolyte injection step S24, a liquid electrolyte or a UV electrolyte is injected into an empty space formed between the upper electrode 20 and the lower electrode 50 after the lower electrode bonding step S23, Or irradiating UV to cure it. The liquid electrolyte and the UV electrolyte contained the electrochromic material 40 as in the first embodiment.

The reaction speed of the electrochromic device can be improved through the upper electrode 20 and the lower electrode 50 of the mesh type in which the electrical conductivity is improved through the first and second embodiments, The following examples will be described.

Any one electrochromic material selected from the first to third compounds and lithium perchlorate was mixed in the electrolyte.

In the first experimental example, a tin oxide conductive film substrate (FTO glass) having a sheet resistance of 8? /? Is used as the upper electrode 20 and the lower electrode 50, and a third compound 0.05 M, and lithium perchlorate (0.05M) were mixed with an electrolyte to form an electrolyte layer (30). In this case, the electrolyte was prepared by using tetramethylene sulfone: propylene carbonate: ethylene carbonate = 30: 40: 30 (v: v: v) As a result, it was confirmed that the color changes in the electrochromic material 40 at a low voltage of 1.5 V as shown in FIG.

The second experimental example of the present invention is the same as that of Example 1 except that an upper electrode 20 having a sheet resistance of 5? /? Having a mesh-like pattern is formed on the glass through an offset, gravure, screen, A third compound 0.05M and lithium perchlorate 0.05M were used as a lower electrode 50 and an electrolyte were mixed to constitute an electrolyte layer 30. [ In this case, the electrolyte was prepared by using tetramethylene sulfone: propylene carbonate: ethylene carbonate = 30: 40: 30 (v: v: v) And the result was confirmed to be driven by the electrochromic material 40 at a low voltage of 1V. In this case, the line-to-line spacing between the meshed patterns is 500 mu m, which can be confirmed from the photograph attached to Fig.

In the third experiment example of the present invention, a plastic substrate was printed using a conductive ink using an offset, a gravure, a screen, and an inkjet printing method so as to have a mesh-like pattern, and an upper electrode (having a sheet resistance of 5? 20 and a lower electrode 50 were formed on the electrolyte layer 30. A third compound 0.05M and lithium perchlorate 0.05M were mixed with the electrolyte to form the electrolyte layer 30. In this case, the electrolyte was prepared by using tetramethylene sulfone: propylene carbonate: ethylene carbonate = 30: 40: 30 (v: v: v) And the result was confirmed to be driven by the electrochromic material 40 at a low voltage of 1V. Here, the interval between the meshed patterns has a line width of 300 mu m, which can be confirmed through a photograph attached to Fig.

As described above, according to the present invention, the electrochromic material 40 is contained in the electrolyte and mixed, and at the same time, the upper electrode 20 and the lower electrode 50 are printed with the conductive ink so as to have a mesh-like pattern, Therefore, the time for reaching the concentration level at which the color changes in the electrochromic material 40 can be significantly shortened. That is, since the conductivity of the upper electrode 20 and the lower electrode 50 printed in a mesh form increases and ions moving from the electrolyte to the electrochromic material 40 proceed faster than the conventional electrochromic material 40, This is because the ion concentration level is rapidly increased in the ion-exchange membrane 40.

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 invention as defined in the following claims And changes may be made without departing from the spirit and scope of the invention.

10: upper substrate 20: upper electrode
30: electrolyte layer 40: electrochromic material
50: lower electrode 60: lower substrate

Claims (12)

In an electrochromic device in which the color is changed by an electrical signal,
The electrochromic device comprising: a lower electrode formed on one surface between an upper electrode and a lower substrate formed on one surface of an upper substrate;
An electrolyte layer formed of any one of a liquid, a solid, and a UV electrolyte that transmits an electric signal applied from the upper electrode and the lower electrode; And
And an electrochromic material whose color is changed by an electrical signal applied from the electrolyte,
Wherein the electrochromic material is mixed with the electrolyte in the electrolyte layer and formed between the upper electrode and the lower electrode. The method of claim 1, wherein at least one of the upper electrode and the lower electrode
Wherein the pattern is a mesh pattern printed on one surface of the upper substrate or the lower substrate by a conductive ink by an offset, a gravure, an inkjet, and a screen printing method. The plasma display panel of claim 1, wherein one of the upper electrode and the lower electrode
Wherein the electrochromic device comprises a tin oxide conductive film substrate (FTO). The method of claim 1, wherein the electrolyte layer
The electrochromic material was prepared by mixing 5,10-dihydro-5-methylphenazine and 4-vinylbenzyl chloride in a weight ratio of 1: 1 The first compound,
A second compound in which 5,10-dihydro-5-methylphenazine and methacryloyl chloride are mixed in a weight ratio of 1: 1,
4,4'-bipyridine and methacryloyl chloride are mixed in a weight ratio of 1: 1. The electrochromic device according to claim 1, wherein the first compound is selected from the group consisting of 4,4'-bipyridine and methacryloyl chloride. 5. The electrochromic device of claim 4, wherein the electrochromic material comprises
Wherein the electrochromic device is at least one selected from any one of the first to third compounds and lithium perchlorate. The method of claim 1, wherein the electrolyte comprises
Tetramethylene sulfone, propylene carbonate, and ethylene carbonate are mixed in a ratio of 30: 40: 30 (v: v: v). The method of claim 1, wherein the upper and lower substrates
Plastics, indium oxide and tin oxide substrates having a sheet resistance of 3 to 9? / ?. An upper electrode printing step of printing an upper electrode by conductive ink on one surface of the upper substrate;
An electrolyte printing step of printing an electrolyte on one surface of the upper electrode; And
And a lower electrode bonding step of bonding the lower electrode printed with the conductive ink after the electrolyte printing step to the upper electrode on which the electrolyte is printed,
Wherein the upper electrode and the lower electrode are formed in a mesh pattern having a lattice structure by conductive ink in the upper electrode printing step and the lower electrode bonding step. An upper electrode printing step of printing an upper electrode on a glass, an ITO, an FTO, and a plastic substrate so as to have a mesh-like pattern having a grid structure with an upper electrode by conductive ink;
A lower electrode bonding step of bonding a lower electrode printed in a mesh pattern having a lattice structure to the upper electrode in a lower substrate formed of any one of glass, ITO, FTO and plastic substrate with the conductive ink after the upper electrode printing step; step; And
And injecting a liquid or UV electrolyte between the upper electrode and the lower electrode after the lower electrode bonding step and curing the electrolyte. The method of claim 8 or 9, wherein the upper electrode and the lower electrode
Wherein the mesh type having a lattice structure has a line width of 1 to 20 mu m and a line spacing of 100 to 1000 mu m. 10. The method according to claim 8 or 9,
The electrochromic material was prepared by mixing 5,10-dihydro-5-methylphenazine and 4-vinylbenzyl chloride in a weight ratio of 1: 1 And a second compound in which 5,10-dihydro-5-methylphenazine and methacryloyl chloride are mixed in a weight ratio of 1: 1, , A third compound in which 4,4'bipyridine and methacryloyl chloride are mixed in a weight ratio of 1: 1, and lithium perchlorate. Lt; / RTI > 10. The method of claim 9, wherein in the lower electrode bonding step,
Wherein the upper electrode and the lower electrode are stacked at a predetermined height on opposite sides of each of the opposite surfaces of the upper electrode and the lower electrode, and are injected into a void space formed by adhesion and sealing between the upper electrode and the lower electrode. Way.

Images