JPS61238028A - Electrochromic element - Google Patents

Abstract

PURPOSE:To prevent a generation of a gas from the second electrode, and to enable the drive of the titled element with a low voltage by constituting the first electrode composed of the electrochromic (EC) element with an electroconductive polymer film having the EC effect and adhering to the electroconductive substrate, and by constituting the second electrode with the electroconductive polymer film adhered to the electroconductive substrate. CONSTITUTION:In the EC element, the first electrode 3 of a working electrode is composed of one or more kinds compds. selected from a polyaniline, a polypyrrole and a polythiophene, and having the EC effect and adhering to the electroconductive substrate coated with SnO2 on a metal film or a glass plate. The second electrode 4 composed of the electroconductive polymer and adhered to the electroconductive substrate is arranged so as to intersect with the electrode 3 at right angle. An aqueous solution 5 of perchoric acid is enclosed in the rectangular space formed with the electrodes 3, 4 and the transparent glass plate 61 and the side glass surface 611, as an electrolyte. By constituting the titled element as mentioned above,the generation of H2 or O2 gas in the second electrode is prevented, and the EC element enabling to drive with a low voltage for long periods is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrochromic device that exhibits a color change due to an electrochemical redox reaction, and particularly to a device in which an organic polymer performs an electrochromic action.

[Conventional technology]

In today's information-overloaded society, display technology plays an important role in processing large amounts of information.

Display means are generally divided into active display elements that emit light themselves, such as cathode ray tubes, and passive display elements that do not emit light themselves, such as liquid crystal displays. ,@'s passive devices are attracting attention due to their low power consumption and safety due to the use of natural light.1For example, in the case of liquid crystals, they have a wide range of applications such as calculators2 and watches.

However, since liquid crystals utilize changes in the orientation of polymers, there are limitations in terms of visibility characteristics, brightness, and multi-colorization. Therefore, electrochromic devices have been developed as an alternative to liquid crystals. This chromochromic element produces color changes such as coloring and decoloring through electrochemical redox reactions, and can be applied to optical switches.

Examples of substances having an electrochromic effect include inorganic compounds such as tungsten oxide (WO), organic compounds such as methyl viologen, and conductive polymers such as polypyrrole, polyaniline, and polythiophene. In particular, when using the above-mentioned conductive polymer, it has the advantage that it can be used in a wider range of applications by making it into a membrane, and it is easy to synthesize the membrane and control its area, and it is also possible to increase the area. .

An electrochromic device using this conductive polymer is composed of an electrolyte solution containing a supporting electrolyte and two electrodes that are in contact with it.The conductive polymer is placed on one electrode (working electrode). .

The other t-pole (opposing pole) is made of a metal plate such as platinum. 2
When a voltage is applied to each electrode, the conductive polymer exhibits a color change due to the redox reaction that occurs at the working electrode.

However, since a metal plate is used as the counter electrode when this voltage is applied, a decomposition reaction of the electrolyte solution occurs and gases such as hydrogen or oxygen are generated. This gas inhibits the exchange of electrons between the IT electrode and the electrolyte solution, reducing the effectiveness of the electrochromic device.

Furthermore, the electrochromic device described above also has the problem of requiring a large applied voltage to perform its function.

[Problem that the invention seeks to solve]

The present invention has been made in view of the above-mentioned problems, and aims to provide an electrochromic element that does not generate gas from opposing electrodes and can perform electrochromic action with a small applied voltage. I'll go.

[Means for solving problems]

The electrochromic device of the present invention includes an electrolyte solution,
It consists of a first electrode and a second electrode that are in contact with the electrolyte solution, and the eleventh electrode is composed of a conductive base material and a conductive polymer film exhibiting an electrochromic effect that is in close contact with the conductive base material, and the above-mentioned The second electrode is characterized by comprising a conductive base material and a conductive polymer in close contact with the conductive base material.

The basic configuration of the electrochromic device of the present invention is as follows:
It consists of a pair of electrodes, an electrode and a second electrode, and an electrolyte solution.

First, the electrode consists of a conductive base material and a conductive polymer film exhibiting an electrochromic effect that is closely attached to the conductive base material, and serves as a working electrode. This polymer membrane exhibits electrochromic action.

The conductive base material is a supporting material for the polyaniline film, and also serves to transfer electrons between the power supply for operating the electrochromic device and the polyaniline film.

However, its materials include metals such as stainless steel, platinum, gold, and nickel, as well as ITO (indium tin oxide) film.

Examples include transparent conductive materials such as glass coated with 8nO, a film or a gold-deposited film, or a transparent plastic boom. In particular, when displaying an electrochromic effect through the conductive base material, the conductive base material should be transparent.

In addition, the shape of the base material is plate-like or net-like.

It is desirable to use it in the form of a plated film or a vapor deposited film.

In addition, examples of conductive polymers exhibiting electrochromic action include polyaniline and polybillow.

Examples include polythiophene, and one or more of them may be used in combination of two or more. The polymer is used as a membrane,
The film thickness is preferably within the range of 500 to 2 μm. If the film thickness is less than 500 Å, no noticeable color changes such as coloring or decoloring can be observed.

On the other hand, if the film thickness exceeds 2 μm, it becomes difficult to erase the color.
It is obtained when it is within the range of 00A to 1 μm.

Methods for synthesizing the conductive polymer membrane exhibiting the electrochromic effect include a method of synthesizing by electrolytic polymerization, a method of using a catalyst, and the like.

For example, a method for synthesizing a polyaniline film by electrolytic polymerization involves forming a complete electrolytic polymerization solution in which aniline, aniline monomers such as aniline hydrochloride, and aniline sulfate are dissolved in an acidic aqueous solution such as hydrochloric acid, sulfuric acid, nitric acid, or perchloric acid. , carbon graphite, stainless steel), etc., are immersed in the electrolytic polymerization solution. After that, by applying a DC voltage between the pressure and negative electrodes, it is desirable that the voltage is within the range of Boriani above the positive 'It pole, and optimally α1~2aw4/
Ruru within the range of 1. In addition, Ani# in the solution for electrolytic polymerization,
The concentration of the phosphorus monomer is preferably within the range of (L1~5''dll (l), and optimally within the range of α+i; l$444; The voltage is 1 per unit area of the positive electrode.
It is desirable that a current with a current density of 0 μA to 5 mA/nl flows, and optimally the current density is 50 to 500 μA.
It is preferable that it be within the range of μA/.

In addition, when synthesizing a polypyrrole membrane or a polythiophene membrane by polymerization, an electrolytic polymerization solution is prepared in which a supporting electrolyte and a pyrrole monomer or a thiophene monomer are dissolved in a solvent.As the supporting electrolyte, Potassium chloride, sodium chloride, lithium perchlorate, potassium perchlorate, silver perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetrafluoroborate, Examples of the solvent include water, methanol, ethanol, acetonitrile, propylene carbonate, etc. In this MU for electrolytic polymerization, a positive electrode made of carbon graphite, stainless steel, etc. Immerse the negative electrode.

Thereafter, by applying a DC voltage between the positive and negative electrodes, a polypyrrole film or a polythiophene film is deposited on the positive electrode. In addition, in this case, the electrolyte.

A range of 1/4 is good. The concentration of pyrrole monomer or thiophene monomer in the solution is preferably such that the current density is [11 to 10 mA-/1-11] per unit area of the α01 positive electrode, and optimally 1 to 10 mA-/1-11. 7mA/l*
It is better to be within the range of .

The method for bringing the polymer film into close contact with the conductive base material is as follows:
There are methods such as compression bonding or vapor deposition.

In addition, as mentioned above, a method uses a conductive base material as a positive electrode for electrolytic coupling of a polymer membrane, and takes advantage of the fact that the polymer membrane is deposited on the conductive base material of the positive electrode during electrolysis. etc. However, it is desirable to use electrolytic polymerization from the viewpoint of adhesion and film formability.

The second #L pole is composed of a conductive base material and a conductive polymer that is in close contact with the conductive base material, and serves as a counter pole.

The four-electroconductive base material has the same function as the conductive base material of the first electrode, and is made of a metal such as stainless steel or platinum like the one in the first electrode.

ITO film, 8nO! In addition to transparent conductive materials such as glass or transparent plastic film coated with a film or gold-deposited film, carbon and graphite can also be used. It is desirable to use the shape of a plate, a net, a plated film, or a vapor deposited film.

Further, the conductive polymer causes an oxidation/reduction reaction when the electrochromic element is operated, and has the function of suppressing gas generation unlike conventional metal electrodes. , as the conductive polymer, polyaniline, polypyrrole,
Examples include polythiophene, and one or more of them may be used. In addition, in the case of two or more kinds, a copolymer, a mixed polymer, or a material containing both a copolymer and a mixed polymer may be used. Examples of the shape of the polymer include a film-like material and a powder-like material, but a film-like material is preferable in terms of adhesiveness and conductivity. In the case of a film-like body, the film thickness is preferably within the range of 500 A to 10 μm. If the film thickness is less than 500 A, the above-mentioned function of the conductive polymer film will not be fully exerted during operation of the element, Gas may be generated from the electrode soil. On the other hand, if it becomes thicker than 10 μrn.

The resistance of the conductive polymer film increases, and the first electrode and the second
As the applied voltage between the electrodes increases.

Electrochromic reactions become very slow. A more preferable film thickness is within the range of 1oooi to 3pτn.

As a method for synthesizing the above-mentioned conductive polymer, II solution kn
There are methods such as synthesis method using a catalyst and method using a catalyst.

For example, when synthesizing a polyaniline film by 9wt depolymerization, it is desirable to synthesize the polyaniline film of the first electrode under the same conditions as in the case of synthesizing the polyaniline film of the first electrode. When synthesizing the membrane, it is desirable to carry out the synthesis under the same conditions as when synthesizing the first polar polypyrrole membrane or polythiophene membrane.

Methods for bringing the conductive polymer into close contact with the conductive substrate include methods such as pressure bonding or vapor deposition as in the case of the first electrode, as well as methods utilizing electrolytic polymerization. In this case, it is better to use electrolytic polymerization in terms of film formability. In addition.

When the conductive polymer is used in powder form, it may be mixed with a 4-electric material such as carbon and brought into close contact with the conductive base material.

Next, the electrolyte solution according to the present invention allows current to be passed between the first electrode and the second electrode by dipping the two electrodes, and the i1! It is involved in the electromic action of the conductive polymer film at the pole.

The electrolyte solution is a supporting electrolyte dissolved in a solvent.

When a polyaniline membrane is used for the first wL electrode, an acidic aqueous solution in which an acidic supporting electrolyte is dissolved in water is used as the electrolyte solution. This is because hydrogen ions involved in the electrochromic action of the polyaniline film are required in the solution. Hydrochloric acid, sulfuric acid, and nitric acid are used as solutes for the above acidic support.

Examples include perchloric acid and phosphoric acid, and one or more of them are used.

Also, number 1! When a conductive polymer membrane other than polyaniline is used as the electrode, the above-mentioned supporting electrolyte is used.

In addition to the above-mentioned acidic supporting electrolyte, supporting electrolytes used in the electrolytic polymerization of the polypyrrole membrane or polythiophene membrane, such as potassium chloride, sodium chloride, lithium perchlorate, and tetramethylammonium tetra7borate, can also be used. . Therefore, one or more of these supporting electrolytes are used.

In addition, as a solvent, water, methanol, ethanol/L/
, acetonitrile, propylene carbonate, etc., and one or more of them are used.

In this case, there is a possibility that the conductive polymer of the first electrode and the second electrode may be dissolved, or that the supporting electrolyte may not be completely dissolved. Furthermore, if the above-mentioned concentration is within the range of +1.1 to 5□Buichi/e, more excellent responsiveness can be achieved.

Better stability of conductive polymers is obtained.

The electrochromic device of the present invention is arranged such that the electrolyte solution and the first and second electrodes are in contact with each other. Since the electrolyte solution and both electrodes are in contact with each other, all or part of the electrode is actually immersed in the electrolyte solution stored in the container. In addition, for both electrodes, only the conductive polymer film or conductive polymer exhibiting electrochromic action is in contact with the electrolyte solution, and the conductive base material is not in contact with the solution.

If the conductive substrate comes into contact with the solution, gas may be generated during operation of the device. Moreover, the electrolyte solution is.

It may also be impregnated into a water-absorbing polymer such as cellulose or an ion exchange membrane.

The container for storing the electrolyte solution is desirably made of a material that is not susceptible to the electrolyte solution and has electrical insulation properties, such as polyethylene, polypropylene, and glass.

Note that the first electrode and the second electrode should not be in direct contact with each other in the electrolyte solution. Therefore.

An insulator such as a separator such as polypropylene or cellulose, an electrolyte holding material, a spacer, etc. may be arranged between the two electrodes.

The first electrode and the second electrode are each connected to a source by attaching appropriate lead portions.

Next, various examples of arrangement of the first electrode and the second electrode are shown in FIGS. 2 to 6. Although each figure shows only the first electrode and the second electrode in plan view, both electrodes are actually in contact with the electrolyte solution. In the figure, 1 indicates the first electrode, 2 indicates the second electrode, and the arrow indicates the viewing direction. Firstly, pole 1 undergoes an electrochromic reaction and exhibits a change in coloring and decoloring.
The first electric current ff1l is made to exist in the field of vision, and the second electric current ff1l is
7M2 will be placed in a position that is out of sight of Kei.

When the conductive base material 10 of the first 'lc electrode 1 is transparent.

As shown in Figure 2, the poles are arranged in series on both sides, and i9 is the third
As shown in the figure, the two electrodes are positioned at right angles. In both FIGS. 2 and 5, light is blocked when the conductive polymer film of the 11th E electrode is colored, and light is transmitted when it is decolored.

If the conductive base material 11 of the first electrode 1 is opaque, the two electrodes may be arranged in series as shown in FIG. 4, or the electrodes may be arranged at right angles to each other as shown in FIG.

As shown in Figure 6, there is an arrangement in which both electrodes are lined up in parallel.

In both cases, the conductive polymer film of the first electrode 1 is placed in the field of vision. In this case, when the conductive polymer film is decolored, a conductive base material appears, and especially in the case of a base material with a high light reflectance, the base material becomes a mirror surface.

Further, when the conductive polymer film turns #-colored, the base material is hidden.

As mentioned above, when the conductive base material of the first electrode is transparent such as glass coated with an I'I'O film, the electrochromic element of the present invention can be applied as an anti-glare mirror or a light control glass. In addition, when the conductive substrate is opaque such as metal, it can be applied as an anti-glare mirror or a display plate.

The electrochromic element of the present invention exhibits a color change of coloring and decoloring upon application of voltage.9 For example, when a polyaniline film is used as the first electrode, the voltage applied to the first electrode (working electrode) (for the second [pole; the same applies hereinafter) is −α6 V, +(L2V.

+ (At L6V, they appear pale yellow, green, and dark blue, respectively, and by applying an intermediate voltage between them.

Each intermediate color can be obtained. Note that the light yellow color appears visually transparent.

[Action of the invention]

Function of the electrochromic device of the present invention.

A case in which a polyaniline film is used for the first electrode will be described by way of example. The first w of electrochromic elements
A constant voltage power supply is connected between the L pole and the second electrode, and the first
When a voltage of -0.6 V is applied to the electrode, the polyaniline film of the first electrode becomes transparent (light yellow).

Next, when the applied voltage is changed to +0.2V, it becomes transparent (light yellow).
The polyaniline film of the first electrode was colored green.

This is considered to be because polyaniline undergoes an oxidation reaction as shown in the following chemical reaction formula (A).

Furthermore, when a voltage of +0.6v is applied to the first electrode.

The polyaniline film undergoes an oxidation reaction involving the anion (X-) of the supporting electrolyte in the electrolytic solution, as shown in the following chemical reaction formula CB).9. It changed to dark blue again. When a voltage of -0.6 .mu. is applied to the first electrode in this state, the polyaniline film is reduced to polyaniline on the side of the chemical reaction formula (A), and turns pale yellow.

All of the above reactions are electrochemically reversible.

By controlling the applied voltage, it is possible to change the color to a desired color.

In addition, since a conductive polymer is used in the second electrode, which is the opposite electrode, by applying a voltage.

It is thought that an oxidation/reduction reaction of the conductive polymer is occurring.

For example, when a conductive polymer and cytephoria diphosphorus are used as the second electrode, the chemical reaction formula (
The oxidation/reduction reaction of A) and CB) occurs as a reaction opposite to that of the first electrode.
L'? If used.

An oxidation/reduction reaction occurs as shown in the following chemical reaction formula [C] (in the formula, X- represents an anion of the supporting electrolyte in the electrolyte solution). Therefore, a decomposition reaction of the electrolyte solution occurs as in the conventional case. Therefore, the decomposition reaction of the electrolyte solution as in the conventional case does not occur, and gases such as hydrogen or oxygen are not generated.

Further, since this gas is not generated, the overvoltage applied to the second electrode can be reduced, and therefore, the applied voltage for performing the electrochromic action may be small.

〔Effect of the invention〕

According to the present invention, it is possible to provide an electrochromic element that does not generate gas from the opposing electrode by using a conductive polymer for the opposing electrode and can perform electrochromic action with a small applied voltage. can.

Further, the electrochromic device of the present invention is as follows.

Since no gas is generated, it provides stable electrochromic operation and has a long life.

The electrochromic device of the present invention can be applied to anti-glare mirrors of automobiles, 1111 optical glasses, blinds, large display elements, small display elements, light amount adjustment filters, etc.

〔Example〕

The present invention will now be described in detail.

Example 1 An aqueous solution was prepared as an electrolytic polymerization solution, and a glass coated with an ITO film having a thickness of 11111 mm as a positive electrode and carbon as a negative electrode were respectively immersed in the solution.

A voltage was applied between the two electrodes so that a direct current with a current density of 100 μA/1 (per unit area of the positive electrode) was applied to perform electrolytic polymerization. Film thickness approximately 20% on I'l'0 film coated glass
Deposit a 0OA polyaniline film.

These were used as the first electrodes.

Electrolytic polymerization was carried out in the same manner as above, except that A polyaniline film with a film thickness of about 500 OA was deposited on the carbon of the positive electrode, and these were used as the second electrode.

First, the electrochromic element according to the present invention is
It was formed as shown in the figure. Note that FIG. 1 is a perspective view of the element. The electrochromic element is a hollow rectangular body in which a first electrode 3 and a second electrode 4 are arranged at right angles, and both electrodes and transparent glass 61 are arranged to surround the periphery. . Note that 611 and 612 are the side and rear surfaces of the transparent glass, respectively. A 11 m x 4/l perchloric acid aqueous solution 5 was placed in the ob cavity of this rectangular parallelepiped. Note that a polypropylene separator 7 is interposed between the first electrode 5 and the second electrode 40 so that they do not come into contact with each other. Further, only the polyaniline membranes of both electrodes are in contact with the electrolyte solution.

Lead portions 8 were attached to the first electrode 5 and second electrode 4 of this element, respectively, and a constant voltage power source 9 was connected to them.

-IL6V, +12V, to the first electrode 3 of the element.
A voltage of -4-[L6v was applied to each, and the visible light absorption spectrum)/l/ was measured from the direction of the arrow in FIG. 1 to evaluate the spectral characteristics of the first electrode 3. The results are shown in the visible light absorption spectrum curve in Figure 7 (center #!D in the figure).
, E, and F each have an applied voltage of 1 α6v.

This is for the case of +α2v and -1−1lLtsv. )
From the spectrum curve in Figure 7, the polyaniline film of the first electrode is pale yellow (applied voltage -G, 6V) and green (+α2■).
It was found that the color changed to dark blue (10α6v).

For comparison, a comparative electrochromic device similar to the above except that the second TiL electrode was changed to one consisting only of carbon, stainless steel, platinum, gold, and nickel was formed, and the spectrum as shown in Figure 7 was obtained. The applied voltage at the first VT pole necessary to exhibit the characteristics was measured.The results are shown in the table.

As is clear from the table, it can be seen that the element of the present invention can perform electrochromic action at a lower voltage than the comparative electrochromic element.

Table Example 2 This example shows an example in which a polypyrrole film is used for the second electrode.

Electrolytic polymerization was carried out using a 10λ-Rue α2 Mkk4/l sodium perchlorate aqueous solution (per potential area) to deposit a polypyrrole film with a thickness of about 5oon^ on the carbon of the positive electrode.

An electrochromic device similar to that of Example 1 was formed except that the carbon on which the polypyrrole film was deposited was used as the second electrode.

When a voltage was applied to this element, it was possible to cause the same color change with the same applied voltage as in Example 1 when polyaniline was used as the second electrode.

Example 5 In this example, electrochromic OL o, s dktc4I/(l) in an element was immersed in an ITO film-coated glass with a thickness of 1 nm as a positive electrode and carbon as a negative electrode in an aniline aqueous solution, and a current density of 200 μA/ (per unit area of the positive electrode) to deposit a polyaniline film with a thickness of about 40,001 mm on the ITO film-covered glass.The ITO film-covered glass on which this polyaniline film was deposited was used as the first electrode.

Except that to make the second electrode, carbon was used as the positive electrode and the flow density was 1 mA/d.

In the same manner as above, a polyaniline film having a thickness of about 800 OA was deposited on the carbon to form a second electrode.

First, an electrochromic device was formed as shown in FIG. Note that FIG. 8 is a perspective view of the element. The electrochromic element is constructed of a cavity in which a pole 31 and a second electrode 41 are arranged in series, and a transparent plastic 62 surrounds the poles. It is rectangular. Note that 621 and 622 are the side and top surfaces of transparent plastic, respectively. A 3.2 d/l perchloric acid aqueous solution at 5° was placed in the rectangular cavity. Note that a cellulose separator 71 is interposed between the first electrode 31 and the second electrode 41, and only the polyaniline membrane of both electrodes is in contact with the electrolyte solution.

Lead portions 81 were attached to both ′IL poles of this element, and a constant voltage power source 91 was connected.

Step voltages of -α6 and +[L6V were applied to the first pole 31. Note that the holding time at each voltage was 1 second, and voltage changes were repeated.

At this time, the polyaniline film of the first electrode becomes thin iQ when a voltage of -α6V is applied, dark blue when a voltage of +[L6V is applied, and by repeating this voltage change, the color changes from pale yellow to dark blue. <9 returned.

The cycle life of the device was measured by the change in the amount of electricity used over the cycle. That is, the initial quantity of electricity is about 10 rne/d per unit area of the first pole.

Taking this value as 100%, the ratio of the amount of electricity to the initial amount of electricity when the cycle was repeated was measured.

The results are shown in FIG. Also, for comparison, the cycle life results of a comparative element whose second pole is made of only carbon or stainless steel are also shown in the same figure. 81 (for carpon ffi), U shown in curve S2 (for stainless steel) As is clear from FIG. 9, the element of the comparative example.

After 5 x 10'' to 5 x 101 cycles, the electricity amount ratio became about 50% of the initial value, and no color change occurred.

It can be seen that the cycle life is short. At this time, a large amount of gas was generated from above the second electrode.

On the other hand, in the device of the present invention, even in the 2×10' cycle, the electrical quantity ratio was more than 95% of the initial value, and the 9 color changes were performed in the same way as in the initial stage.

It turns out that it has a long life. Note that there is no gas generation from the second electrode.

Example 4 In this example, a polypyrrole film is used as the second electrode, the first electrode and the second electrode are arranged in parallel, and wsoJL acid-15-/! After immersing a 12H thick stainless steel /I/ in an aniline aqueous solution as a positive electrode and carbon as a negative electrode, electrolytic polymerization was performed at a current density of 100 μA/1 (per unit area of the positive electrode) to form a film thick on the stainless steel. Approximately 4 oooi of polyaniline film was deposited. The stainless steel on which this polyaniline film was deposited was used as the first electrode.

rp+os Also, to make the second electrode, [lL2 wxg4/
A thick L2fi+ stainless steel was immersed in a propylene carbonate solution of l lithium perchlorate-α2 m/l pyrrole, with a positive electrode and carbon as a negative electrode.

Electrolytic polymerization was carried out at a current density of 7 mA, increased by 4 (per unit area of the positive electrode), and a polypyrrole film with a thickness of about 1 pm was deposited on stainless steel. The stainless steel on which this polypyrrole film was deposited was used as a WrI2 electrode.

Next, an electrochromic device was formed as shown in FIG. The electrochromic element has a first electrode 5
2 and the second electrode 42 are arranged in parallel, and the two electrodes and the transparent glass 65 are arranged so as to surround the hollow rectangular body. In addition.

631 and 632 are the side and upper m6 sides of the transparent glass, respectively. A 12-/Il sulfuric acid aqueous solution 52 is placed in the cavity. In this example as well, both electrodes are polyaniline membranes that come into contact with the electrolyte solution.

Only polypyrrole film.

Lead portions 82 were attached to both electrodes of this element, and a constant voltage power source 92 was connected.

The cycle life of this element was measured in the same manner as in Example 3. The results are shown in FIG. Also.

The results of a comparative device using only stainless steel as the second electrode are shown in the same figure (the device of the present invention has a curve H
Curve 85 is the second comparative example. ) As is clear from FIG. 11, there is one element of the present invention.

It can be seen that the device has an excellent cycle life compared to the comparative device.

[Brief explanation of drawings]

1 and 7 are perspective views of the electrochromic device of the present invention in Example 1 and diagrams showing visible light absorption spectrum curves of the first electric wire, and FIGS. 2 to 6 are diagrams showing the electrochromic device of the present invention in Example 1. FIGS. 8 and 9 are perspective views and views showing cycle life characteristics of the electrochromic element of the present invention in Example 5, and FIGS. FIG. 11 is a perspective view and a diagram showing cycle life characteristics of the electrochromic device of the present invention in Example 4.

Claims (3)

[Claims] (1) An electrochromic device consisting of an electrolyte solution and a first electrode and a second electrode in contact with the electrolyte solution, the first electrode being a conductive base material and a conductive material that exhibits an electrochromic action in close contact with the conductive base material. 1. An electrochromic device comprising a polymer film, wherein the second electrode comprises a conductive base material and a conductive polymer in close contact with the conductive base material. (2) The electrochromic device according to claim (1), wherein the conductive polymer film exhibiting electrochromic action is made of one or more of polyaniline, polypyrrole, and polythiophene. (3) The electrochromic device according to claim (1), wherein the conductive polymer is one or more of polyaniline, polypyrrole, and polythiophene.