KR100302828B1 - Method for manufacturing electric discoloring device - Google Patents

Abstract

PURPOSE: A method for manufacturing an electric discoloring device is provided to improve response time of the electric discoloring device and extend the life span of the device. CONSTITUTION: An electric discoloring device(100) includes an active electrode(120) on which an electric discoloring layer(110) is coated, an electrolyte layer(140) for electrifying ions according to a variation in voltage, and a reservoir electrode(130) storing ions. The electric discoloring layer is fabricated in such a manner that refined aniline is added to a solution obtained by dissolving electrolyte p-toluenesulfonic acid in distilled water through vacuum distillation to acquire a mixture solution. The active electrode, reservoir electrode and a reference electrode are put in the mixture solution and, simultaneously, polyaniline is deposited on the active electrode, having the potential of the reservoir electrode to the reference electrode is -0.2 to 0.8V. 0.7V is induced to the surface of the active electrode for several minutes to coat the polyaniline on the active electrode.

Description

Manufacturing Method of Electrochromic Device

The present invention relates to a method for manufacturing an electrochromic device, and more particularly, an electrochromic layer applied to an electrochromic device is used by electrochemically synthesizing polyaniline and its derivatives, and polythiophene and its derivatives, which are conductive polymers. And, the electrolyte layer relates to a method of manufacturing an electrochromic device that can maximize the performance of the electrochromic device using a polymer electrolyte having a high electrical conductivity.

In general, electrochromic reversibly controls the color of a material by electrochemical oxidation / reduction reactions. It is the movement of electrons accompanying oxidation or reduction, and it is used to change the energy absorption in the ultraviolet, visible or near-infrared region. It is a phenomenon that causes a change of color accordingly.

The electrochromic apparatus 100 using this phenomenon is coated with an electrochromic layer 110 as shown in FIG. 1, and has a working electrode (Active Electrode) 120 having electrochromic properties, and ions according to a change in voltage. Electrolyte layer 140 and conductive electrode 130 used as a storage of ions (Ion Storage).

Here, the electrochromic layer 110 and the electrolyte layer 140 is classified into a solid type and a liquid type. In the solid type, the electrochromic layer 110 and the electrolyte layer 140 are used in the form of a thin film. Some metal oxides and conductive polymers are used as electrochromic materials, and the liquid type refers to the case of using a solution in which the electrochromic material itself is dissolved in the electrolyte, as in the case of organic discoloring materials (benzidine derivatives and viologen or dipyridine derivatives). .

However, in the case of the liquid type, electrochromic occurs in a dissolved state of the solution, and thus, when a voltage is applied to change the color of the entire solution, a long time is required and power consumption is large. In addition, the electrochromic mirror of the liquid phase has a disadvantage in that the electrochromic device 100 is complicated because a solution may leak when the sealing is not well done, and a thickener and various additives must be used to increase the viscosity of the solution.

On the other hand, the electrochromic layer 110 is a transition metal oxide, an organic color change material, a conductive polymer, and the like, the electrochromic material of the transition metal oxide is divided into a reducing type and an oxidation type again. For example, a reducing (anode) type chromophore that has a color when electrons are reduced such as tungsten trioxide (WO ₃ ) or molybdenum trioxide (MoO ₃ ), and iridium dioxide (IrO ₂ ) or rhodium trioxide (RhO ₃ ) As such, there may be mentioned an oxidizing (cathode) chromophore having a color when the electron is lost and oxidized. Such inorganic materials are deposited in the form of a thin film, which has the advantage of showing electrochromic phenomenon. However, electrochromic properties such as color contrast and oxidation-reduction stability (number of cycles: 10 ⁶ or more) are excellent, but difficult methods such as vacuum evaporation and chemical vapor deposition should be used for thin film production. There is a problem in that a large area display device is difficult to fabricate due to low processability, and there is a problem that technical difficulties are exposed when uniformly coating a thin film or adjusting the thickness of the thin film.

In addition, the organic discoloration material may include a heterocyclic ring or an organic compound having a covalent bond. Examples thereof include Viologen (1,1-disubstituted 4,4′-bipyridinium ions, I), which is known as a herbicide. At this time, the viologen is a reducing chromophore having a color when reduced by obtaining electrons as a dinner with 2,2＇-bipuridyl system or diphthalocyanines, and the radical cations generated when reduced are blue violet. This color change is reversible up to the first reduction reaction and can be repeated and repeated many times without side reactions.

In addition, in the case of the conductive polymer, redox (or doping-undoped) changes the electron density in the covalent bond, thereby allowing the transfer of electrons to a new energy level, thereby facilitating color change.Polyacetylene, polypyrrole, polyaniline , Polythiophene, poly (isothianaphthene), poly (p-phenylenevinylene) and polyfuran are representative examples of electrical discoloration. However, polypyrrole, polyaniline, and polythiophene are stable in the air and have a large color contrast effect, and thus, many studies have been conducted on the practical use, and they have various advantages such as various color changes. This is a highly anticipated material. In addition, since these conductive polymers have unique mechanical and optical properties and processability that other inorganic materials and organic materials do not have, they become a key factor in the present invention described below.

On the other hand, the two reversible electrode is a counter electrode composed of a working electrode 120 consisting of a conductive glass (ITO glass) having an electrochromic property, and a conductive glass (ITO glass) used as a storage of ions (Ion Storage) 130, which is different depending on which electrochromic material is used on the conductive glass (ITO glass). That is, when a reducing chromophoric material (anode type electrochromic material) such as WO ₃ is used as the working electrode 120, an oxidic chromic material made of Ni, Co, or iridium dxide may be used as a relative electrode. In use, the conductive polymer electrode becomes the working electrode 120, and WO _{3, which} is a reducing color material, may be used for the counter electrode 130. The electrochromic device 100 has a simpler structure than the liquid type, and the charge transfer between both electrodes proceeds efficiently so that the electrochromic property and the reversibility of the device become better.

On the other hand, the electrolyte layer 140 is a liquid electrolyte mainly used to perform the function of moving the electrons in accordance with the change of the voltage, such a liquid electrolyte is a reality that is rarely used at present because there is a disadvantage that it is inconvenient to carry and flow down. . In addition, the electrolyte layer 140 must have stable optical properties as a material of non-electrochromic properties as much as possible, and should be transparent and have an ion conductivity in the range of 10 ^-3 to 10 ^-6 S / cm to be used as an electrochromic device. This is possible.

An object of the present invention is to use an electrochromic layer applied to an electrochromic device capable of reversibly controlling the color of a material by electrochemical oxidation / reduction reaction, and a polyaniline, a derivative thereof, a polythiophene, a derivative thereof, and the like. Electrochemical synthesis is used, and the electrolyte layer is made of Polyethyleneimine-SO ₃ ^_ polymer electrolyte or Polyethyleneoxide-ClO ₄ ^- polymer electrolyte to make the response time of the electrochromic device faster and its life longer The present invention provides a method of manufacturing a color changing device.

1 is a schematic view showing an electrochromic device according to the present invention.

Figure 2 is a table showing the conditions of the polymer monomer and the electrolyte, the solvent used in the electrochemical synthesis to implement the electrochromic layer applied to the electrochromic device according to the present invention.

Figure 3 is a chemical structural formula showing the structure of the color change material applied to the electrochromic layer and the counter ion used in the synthesis of the color change material according to the present invention.

4 is a device diagram including a working electrode and a counter electrode installed to implement the electrochromic layer applied to the electrochromic device according to the present invention.

5, 6, and 7 are graphs showing the results of measuring absorption spectra of an electrochromic device to which an electrochromic layer of polyaniline, polyο-toluidine, and polyethoxyaniline according to the present invention are applied at various voltages.

8, 9 and 10 are graphs showing the results of measuring optical responses of an electrochromic device to which an electrochromic layer of polyaniline, polyο-toluidine and polyethoxyaniline according to the present invention is applied.

11 and 12, 13 is a counter ion according to the invention the voltage curve ^{_{- (ClO 4 -, BF 4}} -, PF 4 -) the current of the electrochromic device in accordance with the polyaniline synthesized using the electrochromic layer respectively, Graph representing.

14 and 15, 16 is a counter ion according to the invention find out the optical response of the electrochromic device in accordance with the polyaniline synthesized, each with the electrochromic layer _{^{(ClO 4 -, BF 4 -}} -, PF 4) Graph showing the results of potential pulses measured for

17, 18, and 19 are measured for absorption spectra under various voltages of an electrochromic device fabricated using polythiophene and poly3-methylthiophene according to the present invention as electrochromic layers, respectively. Graph showing the results of the absorption spectrum when doping.

20 and 21 are graphs showing the current-voltage curve of the electrochromic device manufactured by using the polythiophene and poly3-methylthiophene as the electrochromic layer according to the present invention.

22 and 23 are graphs showing the results of potential pulses measured to determine the optical response of an electrochromic device applied as an electrochromic layer of polythiophene and poly3-methylthiophene according to the present invention, respectively.

24 is a chemical structural formula for explaining the polyethyleneim ine-SO ₃ ^_ polymer electrolyte applied to the electrolyte layer of the electrochromic device according to the present invention.

25 and 26 Polyethyleneimine-SO ₃ ^_ applied to the electrolyte layer of the electrochromic device, the other to the invention the polyelectrolyte and Polyethyleneoxide-ClO ₄ ^- a graph showing the results of the measurement of the impedance of the polymer electrolyte.

* Description of the symbols for the main parts of the drawings *

100: electrochromic device 110: electrochromic layer

120: working electrode 130: counter electrode

140: electrolyte layer 150: reference electrode

160: mixed solution

The present invention for achieving the above object, at least the electrochromic layer is coated with a working electrode (electrode) having an electrochromic property, an electrolyte layer for conducting ions according to the change of voltage, and ion storage In the method of manufacturing an electrochromic device consisting of a Reservoir Electrode, the electrochromic layer is, aniline purified by vacuum distillation (Vacuum Distillantion) in a solution of the electrolyte p-toluenesulfonic acid in distilled water ) And then stir with a magnetic stir to obtain a mixed solution, a working electrode made of conductive glass (ITO glass) and a counter electrode made of platinum plate (Fisher Scientific Co.) and the working electrode of the mixed solution. At the same time the reference electrode (Reference Electrode) consisting of a saturated calomel to determine the potential and at the same time the potential of the counter electrode relative to the reference electrode is -0.2 ~ + 0.8V By varying the scanning speed in the range of 20㎷ / sec to deposit a polyaniline (Polyaniline) on the conductive glass, the working electrode, and to induce a voltage of + 0.7V on the conductive glass of the working electrode and leave for several minutes Mass production through coating the polyaniline on the conductive glass is a basic feature of the technical method.

Hereinafter, a preferred embodiment of the manufacturing method of the electrochromic device according to the present invention will be described.

First, in the production of the electrochromic device 100, monomers used in the electrochromic layer 110 include aniline, N-phenyl-1-naphtyanniline, thiophene, 2,2'-bithiophene, 3-methylthiophene, and the like. LiClO ₄ , tetraethylammonium tetrafluoroborate, tetrabutylammonium hexafluorophos-phate, and the like were used as electrolytes to implement the electrochromic layer 110, and acetonitrile and H ₂ O were used as solvents.

In this case, the conditions of the polymer monomer, the electrolyte, and the solvent used in the electrochemical synthesis to implement the electrochromic layer 110 are as shown in Figure 2, the color change of the electrochromic layer 110 implemented through the present invention The structure of the material and the counter ions used in the synthesis of the discoloration material are shown in FIG. 3.

On the other hand, the electrochromic device 100 has a working electrode 120 is coated with an electrochromic layer 110 as described above, having an electrochromic property, an electrolyte layer 140 for conducting ions according to the change of voltage, and In the present invention, a method of manufacturing the electrochromic layer 110 and the electrolyte layer 140 among the elements of the above configuration, and the working electrode 120. The cleaning method of the conductive glass used will be described.

4 is a schematic view for explaining a method of manufacturing an electrochromic device according to the present invention.

Electrochromic layer 110 applied to the manufacturing method of the electrochromic device 100 according to the present invention is largely electrochemical synthesis of polyaniline or electrochemical synthesis of polyaniline derivatives, electrochemical synthesis of polyaniline using a counter ion, using a counter ion It is prepared by electrochemical synthesis of polythiophene, electrochemical synthesis of polybithiophene using counter ions, and electrochemical synthesis of poly3-methylthiophene using counter ions.

In this case, the electrochemical synthesis of the polyaniline is as follows.

Generally, aniline purified through vacuum distillantion is a colorless or pale yellow liquid, and dissolves in alcohol and benzene. First, 0.91 mL (˜0.1 mol) of aniline is dissolved in 100 mL of distilled water. 19.02 g (˜1.0 mol) of toluenesulfonic acid was added to the dissolved solution, and the mixture was stirred with a magnetic stir to obtain a mixed solution 160. Then, the working electrode 120 made of conductive glass (ITO glass) in the mixed solution 160. And a reference electrode 150 made of a platinum plate (Fisher Scientific Co.) and a reference electrode 150 made of saturated calomel for determining the potential of the working electrode 120. A polyaniline is deposited on the conductive glass, which is the working electrode 120, by changing the scan rate to 20 kV / sec in the potential of the counter electrode 130 with respect to Let's do it.

After that, when the voltage is induced about + 0.7V on the conductive glass, which is the working electrode 120, and left for about 20 minutes, it is possible to obtain a conductive glass coated with polyaniline.

In addition, the electrochemical synthesis of the polyaniline derivatives is roughly divided into the electrochemical synthesis of poly-ο-toluidine and the electrochemical synthesis of polyethoxyaniline (Polyethoxyaniline), the electrochemical synthesis of the polyο-toluidine. Synthesis was performed by stirring with a magnetic paddle while adding ο-toluidine purified by vacuum distillation to a solution of 19.02 g (˜1.0 mol) of electrolyte p-toluenesulfonic acid in 100 mL of distilled water to obtain a mixed solution (160). Next, the working electrode 120 made of conductive glass, the counter electrode 130 made of platinum plate, and the reference electrode 150 made of saturated calomel to determine the potential of the working electrode 120 in the mixed solution 160. At the same time, the potential of the counter electrode 130 with respect to the reference electrode 150 is changed to a scanning speed of 20 μs / sec in a range of −0.2 to +0.8 V to convert polyο-toluidine to the working electrode 120. Phosphorus conduction Drift on the glass.

After that, if the voltage is induced about +0.7 on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with polyο-toluidine can be naturally obtained.

In addition, the electrochemical synthesis of the polyethoxyaniline (Polyethoxyaniline) is added 2-ethoxyaniline (ethoxyaniline) purified by vacuum distillation in a solution of 19.02g (˜1.0 mol) of the electrolyte p-toluenesulfonic acid in 100 mL of distilled water. While stirring with a magnetic stir to obtain a mixed solution 160, the working electrode 120 made of conductive glass and the counter electrode 130 made of a platinum plate and the working electrode 120 of the mixed solution 160 At the same time as the reference electrode 150 made of a saturated calomel for determining the potential, the potential of the counter electrode 130 with respect to the reference electrode 150 is set at a scanning speed of 20 kV / sec in the range of -0.2 to + 0.8V. Polyethoxyaniline (Polyethoxyaniline) is deposited on the conductive glass, which is the working electrode (120).

After that, when the voltage is induced about +0.7 on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with polyethoxy aniline can be obtained.

The absorption spectra of the electrochromic device 100 to which the electrochromic layer 110 of polyaniline, polyο-toluidine, and polyethoxyaniline are applied are measured at various voltages. As shown.

That is, the electrochromic device 100 to which the electrochromic layer 110 of polyaniline, polyο-toluidine, and polyethoxyaniline is applied exhibits a color corresponding to the reduced state of the polymer at low voltage (-3V), It can be seen that at high voltage (+ 3V) the color due to the oxidized state appears.

In addition, the results of measuring the optical response of the electrochromic device 100 to which the electrochromic layer 110 of polyaniline, polyο-toluidine, and polyethoxyaniline are applied are shown in FIGS. 8, 9, and 10. appear.

That is, by using a function generator and an oscilloscope, a frequency difference of 1 kHz and a potential difference of +6 V are applied to the electrochromic device 100 so that it can be turned ON (+3 V) and OFF (-3 V) once a second. As a result of measuring the response time and the lifetime (cycle number) by measuring the potential pulse, in the case of the electrochromic device 100 to which the electrochromic layer 110 of polyaniline is applied, as shown in FIG. It can be seen that the cycle number is 3.6 × 10 ⁴ .

In addition, in the case of the electrochromic device 100 to which the electrochromic layer 110 of poly-toluidine was applied, as shown in FIG. 9, the response time was measured at 75 μs, and the number of cycles was 1.5 × 10 ⁴ . As can be seen, in the case of the electrochromic device 100 to which the electrochromic layer 110 of the polyethoxy aniline was applied, as shown in FIG. 10, the response time was measured as 120 μs, and the number of cycles was 1 × 10 ^4. It can be seen that.

On the other hand, the electrochromic layer 110 applied to the manufacturing method of the electrochromic device 100 according to the present invention is roughly divided by the electrochemical synthesis of polyaniline using a counter ion, the electrochemical synthesis of the polyaniline using a counter ion again ClO Electrochemical synthesis of polyaniline with ₄ ^- ions and electrochemical synthesis of polyaniline with BF ₄ ^- ions and electrochemical synthesis of polyaniline with PF ₄ ^- ions.

At this time, the electrochemical synthesis of polyaniline using the ClO ₄ ^- ion is 1.86 in a solution in which 10.6 g (˜1.0 mol) of lithium perchlorate (LiClO ₄ ) of an electrolyte is dissolved in 100 mL of acetonitrile in a solvent. g (˜0.2 mol) of aniline was added to obtain a mixed solution 160, and then the working electrode 120 made of conductive glass and the counter electrode 130 made of platinum plate were added to the mixed solution 160, and While scanning the potential of the counter electrode 130 with respect to the reference electrode 150 while inserting a reference electrode 150 made of a saturated calomel to determine the potential of the working electrode 120 in the range of -0.2 ~ + 0.4V After circulating 20 times while changing the speed to 20 kV / sec, the mixture was left for about 2 hours while maintaining the voltage at +1.2 to + 1.3V to obtain polyaniline powder.

Then, when the voltage is induced about + 1.2V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polyaniline powder can be obtained.

In addition, the electrochemical synthesis of polyaniline using the BF ₄ ^- ion was carried out with 2.17 g (˜0.1 mol) of tetraethylammonium tetrafluoroborate; [CH ₃ (CH ₂ ) ₃ ] in 100 mL of acetonitrile in a solvent. ₄ NPF ₆ ) to obtain a mixed solution 160 by adding aniline to the dissolved solution, and then to the mixed solution 160 a working electrode 120 made of conductive glass and a counter electrode 130 made of platinum plate and At the same time as the reference electrode 150 made of saturated calomel for determining the potential of the working electrode 120, the potential of the counter electrode 130 with respect to the reference electrode 150 is set in the range of -0.2 to + 0.4V. After circulating 20 times while changing to 20 kW / sec, the mixture was left for about 2 hours while maintaining the voltage at +1.3 to +1.4 V to obtain a polyaniline powder.

Then, when the voltage is induced about + 1.4V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polyaniline powder can be obtained.

In addition, the electrochemical synthesis of polyaniline using the PF ₄ ^- ion is tetrabutylammonium hexafluorophosphate; (CH ₃ CH ₂ ) ₄ NBF ₆ of 0.77 g (˜0.02 mol) of electrolyte in acetonitrile of 100 mL of solvent. ) To obtain a mixed solution 160 by adding aniline to the dissolved solution, and then the working electrode 120 made of conductive glass, the counter electrode 130 made of platinum plate, and the working electrode ( A reference electrode 150 composed of saturated calomels for determining the potential of 120 is inserted, and the scan speed is set at a potential of -0.2 to + 0.4V at a potential of the counter electrode 130 with respect to the reference electrode 150. After circulating 20 times while changing to / sec, the mixture was left for several hours while maintaining the voltage at +1.8 to + 2.0V to obtain polyaniline powder.

When the voltage is induced about + 1.8V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polyaniline powder can be obtained.

Here, the counter ion (ClO ₄ ^-, BF ₄ ^-, PF ₄ ^-), each current of the polyaniline synthesized using the electrochromic device 100 is applied to the electrochromic layer 110 - voltage curves 11 and 12, as shown in FIG.

This counter ion by doping that was already present in the polymer backbone due to the dominant effect by making different the generation of the charge carriers and negative charged hwakyulreul _{^{(ClO 4 -, BF 4 -}} -, PF 4).

In addition, the counter ion _{^{(ClO 4 -, BF 4 -}} , PF 4 -) , respectively used to measure the synthesized polyaniline to investigate the optical response of the electrochromic device 100 is applied to the electrochromic layer 110, a potential The results of the pulses are as shown in Figs. 14, 15 and 16.

That is, by using a Function generator flowed 1㎐ times a second ON 1 (+ 3V), results can be OFF (-3V), ClO ₄ ^- electrochromic layer of polyaniline synthesized by using a counter-ion ( In the case of the electrochromic apparatus 100 to which 110) is applied, as shown in FIG. 14, the response time is measured as 50 ms, and the number of cycles is represented as 3.6 × 10 ⁴ , using BF ₄ ⁻ counter ions. In the case of the electrochromic device 100 to which the electrochromic layer 110 of the polyaniline is synthesized, as shown in FIG. 15, the response time is measured as 65 ms, and the number of cycles is represented as 1.5 × 10 ⁴ . PF ₄ ^- in the case of an electrochromic device 100, the electrochromic layer 110 of polyaniline synthesized by using a counter ion is applied, the response time, as shown in Figure 16 is measured in 40ms, can cycle is 6.5 × 10 It can be seen that it is represented by ⁴ .

On the other hand, the electrochromic layer 110 applied to the manufacturing method of the electrochromic device 100 according to the present invention is roughly classified by the electrochemical synthesis of polythiophene using the counter ion, the electrochemical of the polythiophene using the counter ion Synthesis is further divided into electrochemical synthesis of polythiophene using ClO ₄ ⁻ ions, electrochemical synthesis of polythiophene using BF ₄ ⁻ ions and electrochemical synthesis of polythiophene using PF ₄ ⁻ ions.

At this time, the electrochemical synthesis of polythiophene using the ClO ₄ ^- ion 1.7g (~ 0.2 in a solution in which 10.6g (~ 1.0mol) of lithium perchlorate (LiClO ₄ ) of the electrolyte dissolved in 100mL of acetonitrile of the solvent. mol of thiophene was added to obtain a mixed solution 160, and then the working electrode 120 made of conductive glass and the counter electrode 130 made of platinum plate and the working solution were added to the mixed solution 160. While the reference electrode 150 made of saturated calomel for determining the potential of the electrode 120 is inserted, the potential of the counter electrode 130 with respect to the reference electrode 150 is reduced in the range of -0.2 to + 0.4V. After circulating 20 times with 20 s / sec change, the polythiophene powder is obtained by leaving the voltage at +1.6 to +1.7 V for about 2 hours.

Then, when the voltage is induced about + 1.6V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the polythiophene powder coated conductive glass can be obtained.

In addition, the electrochemical synthesis of polythiophene using the BF ₄ ⁻ ions was carried out in 2.17 g (˜0.1 mol) of tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ ) ₃ ] _{4 in} 100 mL of acetonitrile in a solvent. 1.86 g (˜0.2 mol) of thiophene was added to a solution in which NPF ₆ ) was dissolved to obtain a mixed solution 160, and then a working electrode 120 made of conductive glass to the mixed solution 160, and A potential of the counter electrode 130 with respect to the reference electrode 150 is inserted into a counter electrode 130 composed of a platinum plate and a reference electrode 150 composed of saturated calomel for determining the potential of the working electrode 120. After circulating 20 times while changing the scanning speed to -20 to + 0.4V in the range of -0.2 to + 0.4V, the polythiophene powder is obtained by leaving the voltage at +2.1 to + 2.2V for about 2 hours.

Then, when the voltage is induced about + 2.1V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the polythiophene powder coated conductive glass can be obtained.

In addition, the electrochemical synthesis of polythiophene using the PF ₄ ⁻ ions is 0.77 g (˜0.22 mol) of tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) ₄ NBF ₆ ) in 100 mL of acetonitrile in a solvent. 1.7 g (˜0.2 mol) of thiophene was added to the dissolved solution to obtain a mixed solution 160. Then, a working electrode 120 made of conductive glass and a counter electrode made of platinum plate were added to the mixed solution 160. And a potential of the counter electrode 130 with respect to the reference electrode 150 at the same time as the reference electrode 150 composed of a saturated calome to determine the potential of the working electrode 120 and the reference electrode 150. After circulating 20 times while changing the scanning speed to 20 ㎷ / sec in the range of and left for about 2 hours while maintaining the voltage at +2.3 ~ + 2.4V to obtain a polythiophene powder.

Then, when the voltage is induced about + 2.4V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polythiophene powder can be obtained.

On the other hand, the electrochromic layer 110 applied to the manufacturing method of the electrochromic device 100 according to the present invention is roughly classified by the electrochemical synthesis of polybithiophene using a counter ion, The electrochemical synthesis is again performed by electrochemical synthesis of polybithiophene using ClO ₄ ^- ions, electrochemical synthesis of polybithiophene using BF ₄ ^- ions and electrochemical synthesis of polybithiophene using PF ₄ ^- ions. Divided.

In this case, the electrochemical synthesis of polybithiophene using ClO ₄ ⁻ ions is 1.663g (∼) in a solution in which 10.6 g (˜1.0 mol) of lithium perchlorate (LiClO ₄ ) of electrolyte is dissolved in acetonitrile of 100 mL of solvent. 0.01 mol) of bithiophene is added to obtain a mixed solution 160, and then the working electrode 120 made of conductive glass and the counter electrode 130 made of platinum plate are added to the mixed solution 160. While scanning the potential of the counter electrode 130 with respect to the reference electrode 150 while inserting a reference electrode 150 made of a saturated calomel to determine the potential of the working electrode 120 in the range of -0.2 ~ + 0.4V After circulating 20 times while changing the speed to 20 kW / sec, it is left for about 2 hours while maintaining the voltage at +0.9 to + 0.95V to obtain polybithiophene powder.

Subsequently, when the voltage is induced about + 0.9V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polybithiophene powder can be obtained.

In addition, the electrochemical synthesis of polybithiophene using the BF ₄ ⁻ ions was carried out using 1.09 g (˜0.05 mol) of tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ ) ₃ ]) in 100 mL of acetonitrile in a solvent. ₄ NPF ₆ ), 1.66 g (˜0.01 mol) of bithiophene was added to the dissolved solution to obtain a mixed solution 160. Then, the working electrode 120 and platinum of conductive glass were added to the mixed solution 160. The potential of the counter electrode 130 with respect to the reference electrode 150 is placed at the same time as the counter electrode 130 composed of the plate and the reference electrode 150 composed of the saturated calomel for determining the potential of the working electrode 120 are inserted. After circulating about 20 times while changing the scanning speed to 20 kV / sec in the range of 0.2 to + 0.4V, the polybithiophene powder is obtained by standing for 2 hours while maintaining the voltage at + 1V.

Then, when the voltage is induced about + 1V on the conductive glass, which is the working electrode 120, and left for about 20 minutes, the conductive glass coated with the polybithiophene powder can be obtained.

In addition, electrochemical synthesis of polybithiophene using the PF ₄ ⁻ ions was carried out using 0.36 g (˜0.01 mol) of tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) _{4 in} 100 mL of acetonitrile in a solvent. 1.66 g (˜0.01 mol) of bithiophene was added to a solution in which NBF ₆ was dissolved to obtain a mixed solution 160. Then, the working electrode 120 and the platinum plate made of conductive glass were added to the mixed solution 160. A potential of the counter electrode 130 with respect to the reference electrode 150 is placed at the same time as the counter electrode 130 composed of the reference electrode 150 and the reference electrode 150 composed of saturated calomel for determining the potential of the working electrode 120 are inserted. After circulating 20 times while changing the scanning speed to 20 kV / sec in the range of ˜ + 0.4 V, the polybithiophene powder is obtained by being left for about 2 hours while maintaining the voltage at +1.1 to +1.2 V.

After that, when the voltage is induced about + 1.2V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the polybithiophene powder can be obtained.

On the other hand, the electrochromic layer 110 applied to the manufacturing method of the electrochromic device 100 according to the present invention is roughly classified by the electrochemical synthesis of poly3-methylthiophene using a counter ion, the poly3- using the counter ion The electrochemical synthesis of methylthiophene is again carried out by electrochemical synthesis of poly3 methylthiophene using ClO ₄ ^- ions and electrochemical synthesis of poly3-methylthiophene using BF ₄ ^- ions and poly3 using PF ₄ ^- ions. It is divided into electrochemical synthesis of methylthiophene.

At this time, electrochemical synthesis of poly3-methylthiophene using ClO ₄ ^- ion was carried out in 2 mL (1 mL) of a solution of 10.6 g (˜1.0 mol) of lithium perchlorate (LiClO ₄ ) in an electrolyte of 100 mL of acetonitrile. ˜0.2 mol) of 3-methylthiophene is added to obtain a mixed solution 160, and then a working electrode 120 made of conductive glass and a counterpart composed of platinum plate are added to the mixed solution 160. The potential of the counter electrode 130 with respect to the reference electrode 150 is inserted at the same time as the reference electrode 150 including the saturated electrode and the reference electrode 150 that determines the potential of the electrode 130 and the working electrode 120 is inserted. In the range of V, 20 cycles of the scanning speed were changed to 20 kV / sec, and then left for about 2 hours while maintaining the voltage at +1.4 to + 1.5V to obtain poly3-methylthiophene powder.

Then, when the voltage is induced to about 1.4V on the conductive glass, which is the working electrode 120, and left for about 20 minutes, the conductive glass coated with the poly3-methylthiophene powder can be obtained.

In addition, the electrochemical synthesis of poly3-methylthiophene using the BF ₄ ⁻ ions was carried out using 2.17 g (˜0.1 mol) of tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ )) in 100 mL of acetonitrile in a solvent. ₃ ] ₄ NPF ₆ ) was added to 2mL (~ 0.2mol) 3-methylthiophene in a solution to obtain a mixed solution 160, and then the working electrode 120 made of conductive glass in the mixed solution 160 ) And a counter electrode 130 composed of a platinum plate and a reference electrode 150 composed of a saturated calomel for determining a potential of the working electrode 120, and at the same time, the counter electrode 130 with respect to the reference electrode 150. After changing the scanning speed to 20 kV / sec in the range of -0.2 to + 0.4V, the cycle is cycled 20 times and left for about 2 hours while maintaining the voltage at +1.4 to + 1.5V. Get offen powder.

Then, when the voltage is induced about + 1.5V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the poly3-methylthiophene powder can be obtained.

In addition, the electrochemical synthesis of poly3-methylthiophene using the PF ₄ ⁻ ions was carried out with 0.77 g (˜0.02 mol) of tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) _{4 in} 100 mL of acetonitrile in a solvent. 2 mL (˜0.2 mol) of 3-methylthiophene was added to a solution in which NBF ₆ was dissolved to obtain a mixed solution 160. Then, the working electrode 120 and platinum of conductive glass were added to the mixed solution 160. The potential of the counter electrode 130 with respect to the reference electrode 150 is placed at the same time as the counter electrode 130 composed of the plate and the reference electrode 150 composed of the saturated calomel for determining the potential of the working electrode 120 are inserted. After circulating 20 times while changing the scanning speed to 20 kV / sec in the range of 0.2 to + 0.4V, the mixture is left for several hours while maintaining the voltage at +1.5 to + 1.6V to obtain poly3-methylthiophene powder. .

Then, when the voltage is induced about + 1.6V on the conductive glass which is the working electrode 120 and left for about 20 minutes, the conductive glass coated with the poly3-methylthiophene powder can be obtained.

Here, the physical properties of the electrochromic device 100 to which the electrochromic layer 110 of the polythiophene and the poly3-methylthiophene are respectively compared are as follows.

First, the absorption spectra under various voltages of the electrochromic device 100 fabricated by using polythiophene and poly3-methylthiophene as the electrochromic layer 110 were measured, respectively. The results are as shown in Figs. 17 and 18 and 19.

That is, at low voltage (-3V), the electrochromic device 100 showed a color (red) according to the reduced state of the polymer, and at a high voltage (+ 3V), the color (blue) according to the oxidized state, respectively Indicated. As the voltage increased, the peak of the absorption spectrum was shifted to the short wavelength. As a result, the peak of the absorption spectrum was shifted to the short wavelength by excitation.

In addition, the current-voltage curve of the electrochromic device 100 fabricated using the polythiophene and poly3-methylthiophene as the electrochromic layer 110 is shown in FIGS. 20 and 21. That is, in the current-voltage curve of the electrochromic device 100 to which the electrochromic layer 110 of polythiophene was applied, the measured peaks of the oxide and the measured peaks were asymmetric. This is because counter ions existing in the electrolyte solution are doped into the polymer skeleton.

The results of potential pulses measured to determine the optical response of the electrochromic device 100 applied to the electrochromic layer 110 of polythiophene and poly3-methylthiophene are shown in FIGS. 22 and 23. same.

In other words, the function generator is used to flow 1 흘 to enable ON (+ 3V) and OFF (-3V) once per second, and the response time and the number of cycles are measured between the potential difference of 6V. In the case of the electrochromic device 100 to which the electrochromic layer 110 is applied, as shown in FIG. 22, the response time is measured as 71 ms, and the number of cycles is represented as 7 × 10 ³ . In the case of the electrochromic device 100 to which the electrochromic layer 110 using methylthiophene is applied, as shown in FIG. 23, the response time is measured as 100 ms, and the number of cycles is 2.5 × 10 ³ . have.

Meanwhile, the electrolyte layer 140 applied to the method of manufacturing the electrochromic device 100 according to the present invention dissolves 1.OOg of Polyethyleneimine in 10mL of ethanol and 2.00g of 2-acrylamido-2-in 30mL of ethanol at the same time. After dissolving methylpropanesulfonic acid, the solution containing the polyethyleneimine was added to the solution containing 2-acrylamido-2-methylpropanesulfonic acid and stirred for about 1 hour with a magnetic spoon to give a clear turquoise as shown in FIG. 24. Polyethyleneimine-SO ₃ ^_ polyelectrolyte can be used, or 50 mL of propylene carbonate solution is mixed with 50 mL of ethylene carbonate solution and stirred with a magnetic paddle while maintaining a temperature of 100 ° C. with 10.6 g of lithium perchlorate (LiClO). ₄ ) to obtain a mixture, the mixture was slowly added to 50 mL of acetonitrile purified and 4 g of polyethylene oxide was added at a ratio of 1.5: 1. Polyethyleneoxide-ClO ₄ ^- polymer electrolyte can be used.

In this case, the Polyethyleneimine-SO ₃ ^_ polyelectrolyte and Polyethyleneoxide- ClO ₄ ^- results of the measurement of the impedance of the polymer electrolyte is shown in Fig. 25 and 26.

That is, as shown in FIG. 25, the polyethyleneimine-SO ₃ ^_ polymer electrolyte does not exhibit an ideal half circle spectrum having internal resistance starting from 0 and a resistance value of 5.8 × 10 Ω, as shown in FIG. 26. Polyethyleneoxide-ClO ₄ ^- impedance spectrum in the form of a polymer electrolyte but is a non-ideal shape compared with the Polyethyleneimine-SO ₃ ^_ polymer electrolyte resistance exhibited a low value of 780Ω.

In this case, the ionic conductivity of the polyethyleneimine-SO ₃ ^_ polymer electrolyte is 3.18 × 10 ^-6 S / cm from the impedance results of FIGS. 25 and 26, and the ionic conductivity of the polyethyleneoxide-ClO ₄ ^- polymer electrolyte is 1.478 × 10 ^-5. It can be seen that each is S / cm.

On the other hand, the conductive glass used as the working electrode 120 is very important in the production of the electrochromic device 100 because the polymer is directly coated with the electrochromic layer 110, depending on the conditions of the conductive glass Since it greatly affects the stability of the electrochromic device 100 and the like, impurities should be removed as cleanly as possible. When the process is described, first, the dust remaining on the surface of the conductive glass is blown with nitrogen gas, and then the concentration is adjusted to 6wt%. The conductive glass is then washed again in an ultrasonic cleaner using a sodium hydroxide solution containing anionic and nonionic surfactants and additives.

After that, the distilled water is changed three times in the ultrasonic cleaner, and then the conductive glass is washed, and then again washed with ethanol and dried using nitrogen gas to obtain and use the conductive glass having the best conditions. .

As described above, according to the method of manufacturing an electrochromic device according to the present invention, an electrochromic layer applied to an electrochromic device capable of reversibly controlling the color of a material by an electrochemical oxidation / reduction reaction may include a polyaniline as a conductive polymer and By using an electrochemical synthesis of the derivatives, polythiophene and derivatives thereof, the response time of the electrochromic device is faster, the lifespan (the number of cycles) is longer, and there is an excellent effect of realizing various colors.

Also, Polyethyleneimine-SO has a high electrical conductivity of the electrolyte layer is applied to the electrochromic device ₃ ^_ polyelectrolyte or Polyethyleneoxide-ClO ₄ ^- Excellent capable of further improving the response time and the number of cycles of the electrochromic device by the use of the polymer electrolyte It works.

In addition, there is a useful effect of greatly improving the stability and response time of the electrochromic device by removing impurities remaining on the surface of the conductive glass, which is a working electrode applied to the electrochromic device.

In addition, the electrochromic glass window using the electrochromic device can be used as a window of a building, an aircraft, a ship, and has a practical effect of arbitrarily controlling strong light, solar heat, and ultraviolet light entering the room.

In other words, it is possible to control the transmittance of strong light or solar heat entering the room, so in the cold season, the electrochromic layer is transparently controlled so that the maximum solar heat enters the room, and in the hot summer, the sun rays reflect the electrochromic layer. By doing so, it is possible to prevent the room temperature from increasing, thereby effectively controlling cooling and heating.

In addition, by applying to the rearview mirror of the car can prevent the phenomenon of obstructing the driver's vision due to the strong light irradiated from the rear vehicle at night driving, there is an effect that can ensure the driver's safe driving.

In this way, the electrochromic device obtained by the manufacturing method of the present invention can give a lot of benefits to the real life through various applications and practical use, not only can save energy, but also has an excellent effect to bring out a stylish atmosphere. .

Claims (18)

It is composed of a working electrode (electrode) having at least an electrochromic layer coated with an electrochromic property, an electrolyte layer that conducts ions according to a change in voltage, and a reservoir electrode (Ion Storage). In the method of manufacturing the electrochromic device, The electrochromic layer, Adding aniline purified through vacuum distillantion to a solution of electrolyte p-toluenesulfonic acid in distilled water and then stirring with a magnetic spoon to obtain a mixed solution; A working electrode made of conductive glass (ITO glass) and a counter electrode made of platinum plate (Fisher Scientific Co.) and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed in the mixed solution. Depositing polyaniline on the conductive glass as the working electrode by changing the scanning speed to 20 kW / sec in the range of the potential of the counter electrode relative to the reference electrode from -0.2 to + 0.8V; The method of manufacturing an electrochromic device, characterized in that by massing the voltage + 0.7V on the conductive glass as the working electrode and left for several minutes to coat the polyaniline on the conductive glass. The method of claim 1, The electrochromic layer, Adding ο-toluidine purified by vacuum distillation to a solution of electrolyte p-toluenesulfonic acid in distilled water and stirring with a magnetic spoon to obtain a mixed solution, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. Depositing poly-ο-toluidine on the conductive glass, which is the working electrode, by changing the scanning speed to 20 kV / sec in the range of 0.8 V, The method of manufacturing an electrochromic device, characterized in that by producing a voltage of about +0.7 on the conductive glass as the working electrode and left for several minutes to coat the poly-toluidine on the conductive glass. The method of claim 1, The electrochromic layer, Adding purified 2-ethoxyaniline (ethoxyaniline) through vacuum distillation in a solution of electrolyte p-toluenesulfonic acid in distilled water and then stirring with a magnetic spoon to obtain a mixed solution, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. Depositing polyethoxyaniline on the conductive glass, which is the working electrode, by changing the scanning speed to 20 kV / sec in the range of 0.8 V, A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by +0.7 and left for several minutes to coat the polyethoxyaniline on the conductive glass. The method of claim 1, The electrochromic layer, Polyaniline using counter ion (ClO ₄ ^_ ) to obtain a mixed solution by adding aniline to a solution in which electrolyte Lithium Perchlorate (LiClO ₄ ) was dissolved in solvent acetonitrile. Synthesis step, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polyaniline powder was obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.2 to + 1.3V to obtain a polyaniline powder, A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.2V and left for several minutes to coat the polyaniline powder on the conductive glass. The method of claim 1, The electrochromic layer, Counter ion (BF ₄ ) to obtain a mixed solution by adding aniline to a solution of electrolyte tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ ) ₃ ] ₄ NPF ₆ ) in acetonitrile. Synthesis of polyaniline using ^_ ), In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. Obtaining a polyaniline powder by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.3 to + 1.4V; A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by about 1.4V and left for several minutes to coat the polyaniline powder on the conductive glass. The method of claim 1, The electrochromic layer, Counter ion (PF ₆ ) to obtain a mixed solution by adding aniline to a solution in which tetrabutylammonium hexafluorophosphate (CH ₃ CH ₂ ) ₄ NBF ₆ ) was dissolved in a solvent acetonitrile. Synthesis of polyaniline using ^_ ), In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. Obtaining a polyaniline powder by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.8 to + 2.0V; A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.8V and left for several minutes to coat the polyaniline powder on the conductive glass. The method of claim 1, The electrochromic layer, Polythiophene using a counter ion (ClO ₄ ^_ ) to obtain a mixed solution by adding thiophene to a solution in which electrolyte lithium perchlorate (LiClO ₄ ) was dissolved in a solvent acetonitrile. Synthesis step, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polythiophene powder was obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.6 to + 1.7V; A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.6V and left for several minutes to coat the polythiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Counter ion (BF) to obtain a mixed solution by adding thiophene in a solution of electrolyte tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ ) ₃ ] ₄ NPF ₆ ) in a solvent acetonitrile. Synthesis of polythiophene using ₄ ^_ ), In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polythiophene powder was obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +2.1 to + 2.2V; The method of manufacturing an electrochromic device, characterized in that by producing a voltage of about + 2.1V on the conductive glass as the working electrode and left for several minutes to coat the polythiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Poly with counter ion (PF ₆ ^_ ) to obtain a mixed solution by adding thiophene in a solution of electrolyte tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) ₄ NBF ₆ ) in solvent acetonitrile. Synthesis of thiophene, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polythiophene powder was obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +2.3 to + 2.4V; The method of manufacturing an electrochromic device, characterized in that by producing a voltage of + 2.4V on the conductive glass as the working electrode and left for several minutes to coat the polythiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Polybithiophene using counter ion (ClO ₄ ^_ ) to obtain a mixed solution by adding bithiophene to a solution in which electrolyte lithium perchlorate (LiClO ₄ ) is dissolved in a solvent acetonitrile. ) Synthesis stage, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. Obtaining a polybithiophene powder by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +0.9 to + 0.95V; A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by about 0.9V and left for several minutes to coat the polybithiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Solvent acetonitrile electrolyte tetraethylammonium peulroreo borate in _{([CH 3 (CH 2)} 3] 4 NPF 6) the dissolved counterions for obtaining a mixed solution by adding a bar ET thiophene (bithiophene) in a solution (Counter ion; Synthesis of polybithiophene using BF ₄ ^_ ), In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polybithiophene powder is obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at + 1V; The method of manufacturing an electrochromic device, characterized in that by producing a voltage of + 1V on the conductive glass as the working electrode and left for several minutes to coat the polybithiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Using counter ion (PF ₆ ^_ ) to obtain a mixed solution by adding bithiophene in a solution of electrolyte tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) ₄ NBF ₆ ) in a solvent acetonitrile. Synthesis of polythiophene, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A polybithiophene powder was obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.1 to + 1.2V; A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.2V and left for several minutes to coat the polybithiophene powder on the conductive glass. The method of claim 1, The electrochromic layer, Poly3 using a counter ion (ClO ₄ ^_ ) to obtain a mixed solution by adding 3-methylthiophene to a solution in which electrolyte lithium perchlorate (LiClO ₄ ) was dissolved in a solvent acetonitrile. -Synthesis of methyl 3-methylthiophene, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A poly-methylthiophene powder was obtained by circulating a plurality of times while changing the scanning speed in the range of 0.4V to 20 kV / sec and maintaining the voltage at +1.4 to + 1.5V for several hours to obtain poly3-methylthiophene powder, A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by about 1.4V and left for several minutes to coat the poly3-methylthiophene powder on the conductive glass. . The method of claim 1, The electrochromic layer, Counter ion (BF) to obtain a mixed solution by adding 3-methylthiophene in a solution of electrolyte tetraethylammonium tetrafluoroborate ([CH ₃ (CH ₂ ) ₃ ] ₄ NPF ₆ ) in solvent acetonitrile. ₄ ^_ ) synthesis of poly3-methylthiophene, In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A poly-methylthiophene powder was obtained by circulating a plurality of times while changing the scanning speed in the range of 0.4V to 20 kV / sec and maintaining the voltage at +1.4 to + 1.5V for several hours to obtain poly3-methylthiophene powder, A method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.5V and left for several minutes to coat the poly3-methylthiophene powder on the conductive glass. . The method of claim 1, The electrochromic layer, Counter ion (PF ₆ ^_ ) to obtain a mixed solution by adding 3-methylthiophene in a solution of electrolyte tetrabutylammonium hexafluorophosphate ((CH ₃ CH ₂ ) ₄ NBF ₆ ) in a solvent acetonitrile. Synthesis of poly3-methylthiophene using In the mixed solution, a working electrode made of conductive glass, a counter electrode made of platinum plate, and a reference electrode made of saturated calomel for determining the potential of the working electrode were placed, and the potential of the counter electrode with respect to the reference electrode was -0.2 to +. A poly-methylthiophene powder obtained by circulating a plurality of times at a scanning speed of 20V / sec in the range of 0.4V and leaving it for several hours while maintaining the voltage at +1.5 to + 1.6V; The method of manufacturing an electrochromic device, characterized in that the voltage is induced on the conductive glass as the working electrode by + 1.6V and left for several minutes to coat the poly3-methylthiophene powder on the conductive glass. . The method of claim 1, The electrolyte layer, Dissolving Polyethyleneimine in ethanol and simultaneously dissolving 2-acrylamido-2-methylpropanesulfonic acid in separate ethanol, The polyethyleneimine is a polyethyleneimine-SO ₃ ^_ polyelectrolyte obtained by adding a solution containing Polyethyleneimine to the solution containing 2-acrylamido-2-methylpropan esulfonic acid and stirring with a magnetic straw for several hours. Method of manufacturing a color fading device. The method of claim 1, The electrolyte layer, Mixing the ethylene carbonate solution with the propylene carbonate solution and stirring with a magnetic spoon; Maintaining the temperature of 100 ℃ to add a lithium perchlorate (LiClO ₄ ) to obtain a mixture, Method for producing an electrochromic device, characterized in that the polyethyleneoxide-ClO ₄ ^- polymer electrolyte obtained by slowly adding the mixture to purified acetonitrile (acetonitrile) and then adding Polyethylene oxide. The method according to any one of claims 1 to 15, Conductive glass used as the working electrode, Blowing with nitrogen gas to remove dust from the surface; Washing in an ultrasonic cleaner using a sodium hydroxide solution containing anionic and nonionic surfactants and additives adjusted to a concentration of 6wt%, Washing and replacing distilled water multiple times in the ultrasonic cleaner; Washing with ethanol, Method for producing an electrochromic device, characterized in that it is used by washing and drying through the step of drying using nitrogen gas.