JP2000250074A - Electrochromic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an entirely solid electrochromic device excellent in responsiveness. SOLUTION: Transparent electrode layers 2a, 2b are formed on the opposite faces of a pair of transparent substrates 1a, 1b, electrochromic layers 3, 4 are formed on the surfaces of the transparent electrode layers 2a, 2b and a solid electrolyte layer 5 formed from a protonic electrically conductive gelled electrolyte is held between both the electrochromic layers to obtain the objective electrochromic device having equal to or less than 1 sec response speed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic display (EC) which is a display element utilizing an electrochromic (hereinafter referred to as "EC") phenomenon in which the color of a substance is reversibly changed by a voltage applied to the substance.
The present invention relates to an EC device used in D) and the like, and particularly to an all-solid-state EC device having excellent responsiveness.

[0002]

2. Description of the Related Art An EC device utilizes an electrochemical reaction in which a substance is oxidized or reduced by applying a voltage, and utilizes a phenomenon in which the color of the substance is reversibly changed with the reaction. Attempts have been made to apply it to display elements, light control bodies, transmittance variable filters, and the like. This EC element has a basic configuration as schematically shown in a longitudinal sectional view in FIG.

[0003] That is, the EC element is composed of a pair of transparent substrates,
For example, a transparent electrode layer, for example, ITO (Indium Tin) is formed on each of the facing surfaces of the glass substrates 10a and 10b.
Oxide; indium oxide-tin oxide (In ₂ O ₃ —S
nO ₂ )) forming electrode layers 12a and 12b, and forming a first EC layer 13 on the surface of each of the ITO electrode layers 12a and 12b.
And a second EC layer 14 are formed to form both EC layers 13, 1
It has a laminated structure provided so as to sandwich the electrolyte layer 15 between the four. Alternatively, a pair of transparent substrates, for example, glass substrates 20a, 20a,
0b, a transparent electrode layer such as IT
An O electrode layer 21 is formed and the other glass substrate 2
The counter electrode layer 22 is formed on the opposite surface side of the ITO electrode layer 2b.
1 has a laminated structure in which an EC layer 23 is formed on the surface of the substrate 1 and an electrolyte layer 24 is sandwiched between the EC layer 23 and the counter electrode layer 22. A white background plate 25 is provided on the electrolyte layer 24. There is also an EC element having such a configuration. The former EC element shown in FIG. 6 is a complementary element in a transmission type display mode, and the latter EC element shown in FIG. 7 is a charge transfer type element in a reflection type display mode.

In the EC device, electrolyte layers 15 and 24 are provided.
There is a type using a liquid electrolyte and a type using a solid electrolyte. Examples of EC elements using a liquid electrolyte include:
TO glass substrate (glass substrate / ITO film) / WO ₃ (E
C material) / LiClO ₄ -propylene carbonate (electrolyte) / white background plate / carbon electrode (counter electrode material) / IT
O glass substrate (ITO film / glass substrate)
A charge transfer type EC device, in which a WO ₃ film as an EC layer is formed on an ITO film on a glass substrate by vacuum deposition and an activated carbon cloth is pasted on the ITO film on the glass substrate with a carbon paste to form a counter electrode layer, is used as an electronic component. Materials for Materials Research Group CPM8
6-108 (Telecommunications Society of Japan). Also,
ITO glass substrate (glass substrate / ITO film) / WO ₃ /
LiClO ₄ -propylene carbonate / V ₂ O ₅ (E
C material) / ITO glass substrate (ITO film / glass substrate)
And a WO ₃ film as an EC layer and V ₂ O ₅
Complementary EC devices each having a film formed by a sol-gel method are used in Thin Sol Films (Thin Sol).
id Films), 293, 108-112 (199)
7). E using these liquid electrolytes
The response speed of the C element is ensured to some extent, for example, 30 seconds per one cycle of coloring and decoloring.
In the element, since the electrolyte is a solution, the packing process is complicated, and there is a great problem that there is a possibility that the liquid leaks from the seal portion or the liquid leaks when it is broken.

On the other hand, as an example of an EC device using a solid electrolyte, an ITO glass substrate (glass substrate / ITO film) /
It has a structure of WO ₃ / Sb ₂ O ₃ .nH ₂ O (electrolyte) / carbon electrode, and a WO ₃ film as an EC layer is formed on an ITO film of a glass substrate by vacuum deposition, and an electrolyte layer and a carbon electrode layer are formed. EC element formed by a screen printing, electronic technology, is disclosed in 26,59 (1984), also, ITO glass substrate (glass substrate / ITO film / _IrO X (EC material) / _Ta 2 _{O 5} (electrolyte ) / WO
A complementary EC device having a ₃ / Al configuration and all layers formed by vacuum evaporation or sputtering is provided by Proceedings of Japan Display (Proceed).
edings of Japan Display) '
86, 372 (1986). Also, I
TO glass substrate (glass substrate / ITO film) / WO ₃ / L
i-ion gel electrolyte / CeO ₂ —TiO ₂ (EC material)
/ EC with a structure of / ITO glass substrate (ITO film / glass substrate), each layer formed by sol-gel method
The element is a Journal of Non-Crystalline Solid.
line Solids), 218, 185-188
(1997). Further, for example, JP-A-10-232413 discloses a polymer solid electrolyte containing a redox material as an electrolyte layer sandwiched between a substrate provided with an electrode provided with an EC layer and another substrate provided with an electrode. An EC device using a polymer solid electrolyte obtained by curing urethane acrylate and not requiring a counter electrode material layer is disclosed.

[0006]

An EC element having an electrolyte layer formed by using a solid electrolyte is made of an all-solid type, so that when an EC element using a liquid electrolyte leaks or breaks from a sealing portion like an EC element using a liquid electrolyte. The problem of liquid leakage is eliminated, and the manufacturing process is simplified as compared with an EC device using a liquid electrolyte. However, an all-solid-state EC device using a solid electrolyte has poorer responsiveness than an EC device using a liquid electrolyte, such as a response speed of 10 minutes or more.

[0007] The present invention has been made in view of the above-mentioned circumstances, and is directed to an all-solid-state EC using a solid electrolyte.
It is an object to provide an EC element having excellent responsiveness.

[0008]

The invention according to claim 1 is
In an EC device in which an electrode layer is formed on each of the opposing surfaces of a pair of substrates and an EC layer and a solid electrolyte layer are sandwiched between the two electrode layers, the solid electrolyte layer is formed of a proton-conductive gel electrolyte, and the response speed is increased. Is within 1 second.

[0009] The invention according to claim 2 is the invention according to claim 1.
In the C element, each substrate was formed of a transparent material, each electrode layer was formed of a transparent conductive material, and a solid electrolyte layer was provided between the first EC layer and the second EC layer. That is, transparent substrate / transparent electrode layer / first
EC layer / solid electrolyte layer / second EC layer / transparent electrode layer /
It is a complementary element having a configuration of a transparent substrate.

According to a third aspect of the present invention, in the EC device according to the first or second aspect, each substrate is formed of an organic-inorganic hybrid material, and each substrate has flexibility. And

According to a fourth aspect of the present invention, in the EC device according to the first or second aspect, each substrate is formed of a plastic material, and each substrate has flexibility.

According to a fifth aspect of the present invention, there is provided the EC device according to any one of the first to fourth aspects, wherein carbon, oxygen, silicon, sulfur, and phosphorus are used as the proton conductive gel electrolyte forming the solid electrolyte layer. And a substance containing one or more elements selected from the group consisting of hydrogen and hydrogen.

According to a sixth aspect of the present invention, in the EC device according to any one of the first to fifth aspects, the EC layer is an amorphous film.

According to a seventh aspect of the present invention, in the EC device according to any one of the first to sixth aspects, the EC layer and the solid electrolyte layer formed of the proton-conductive gel electrolyte are each composed of a metal alkoxide or a metal alkoxide. It is an amorphous film formed by a sol-gel method using a salt as a raw material.

According to an eighth aspect of the present invention, in the EC device according to any one of the first to seventh aspects, the electrochromic layer has a thickness of 50 μm to 1 μm.

According to a ninth aspect of the present invention, there is provided the EC device according to any one of the first to eighth aspects, wherein the proton conductive gel electrolyte forming the solid electrolyte layer is formed of an alkoxysilane having a polyethylene glycol chain. A substance containing a hydrolyzate or a hydrolyzed polycondensate and containing a sulfate group or a phosphate group is used.

The E of each of the inventions according to claims 1 to 9
Since the electrolyte layer of the C element is solid, there is no danger of liquid leakage from the seal portion or liquid leakage at the time of breakage, and the production process is relatively simple. The response speed is within 1 second and excellent in responsiveness due to the formation of the conductive gel electrolyte. It is considered that the high response speed of the EC element is due to the formation of the electrolytic double layer in the proton conductive gel electrolyte forming the solid electrolyte layer when a voltage is applied. In this regard, FIGS. 4 and 5
This will be described based on the schematic diagram shown in FIG.

FIGS. 4 and 5 are schematic views showing the laminated structure of the EC element. FIG. 4 shows a state where no voltage is applied, and FIG. 5 shows a state where a voltage is applied. I have. In these figures, reference numerals 30a and 30b denote electrode layers, for example, ITO electrode layers, respectively, and reference numerals 31a and
Reference numeral 31b denotes an EC layer, for example, 31a denotes a vanadium oxide layer, 31b denotes an iridium oxide (which may be in the form of hydroxide) layer, and 32 denotes a proton conductive gel electrolyte, in the illustrated example, a sulfate group. The solid electrolyte layer formed by the material containing the
Shows a DC power supply and a switch, respectively. In these drawings, illustration of a pair of substrates is omitted.

The ITO electrode layer 30a of the EC element, when no voltage is applied between 30b, as shown in FIG. 4, HSO ₄ in the solid electrolyte layer 32 in ^- ions and _{H 3}
O ⁺ ions are dispersed throughout the layer. In FIG. 4, HSO ₄ ^- show only dispersion state of the _{ion, H} 3 O
The illustration of the dispersion state of ⁺ ions is omitted. Then, as shown in FIG. 5, when a voltage is applied between the ITO electrode layers 30a and 30b, H ₃ O ⁺ ions and HSO ₄ ⁻ ions move in the solid electrolyte layer 32, and H ₃ O ⁺
Ions and HSO ₄ ⁻ ions are converted to the vanadium oxide layer 31.
a and the iridium oxide layer 31b, respectively, to form an electrolytic double layer in the gel electrolyte of the solid electrolyte layer 32. In this state, insertion of protons (H ⁺ ) into the vanadium oxide layer 31a and extraction of protons (H ⁺ ) from the iridium oxide layer 31b are performed, and the vanadium oxide layer 31a is colored by a reduction reaction, and is oxidized by an oxidation reaction. The iridium oxide layer 31b is colored. When a positive / negative reverse potential is applied between the ITO electrode layers 30a and 30b, a reverse reaction occurs, and the colors of the vanadium oxide layer 31a and the iridium oxide layer 31b disappear and return to a transparent state. Thus, it is considered that the response speed is increased by the formation of the electrolytic double layer in the gel electrolyte of the solid electrolyte layer 32 when a voltage is applied between the ITO electrode layers 30a and 30b of the EC element.

Further, the EC element according to each of the third and fourth aspects of the present invention has flexibility and can be reduced in weight. Furthermore, in the EC element according to the third aspect of the present invention, since a heating process is possible, it is possible to improve the characteristics of the transparent electrode and the EC material.

In the EC device according to the sixth aspect of the present invention, the EC
If a heat treatment is required when forming the layer, the heating temperature may be lower.

In the EC device according to the seventh aspect of the present invention, the heating temperature for forming the EC layer and the electrolyte layer by the sol-gel method may be low.

In the EC device according to the present invention, an appropriate color density is obtained when a voltage is applied.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a preferred embodiment of the present invention will be described with reference to FIGS.

FIG. 1 is a longitudinal sectional view showing an example of the embodiment of the present invention and schematically showing an EC element. This EC
The device has transparent electrode layers 2a and 2b formed on the respective opposing surfaces of a pair of transparent substrates 1a and 1b. An EC layer 3 made of EC material A is provided on the surface of one transparent electrode layer 2a. An EC layer 4 made of EC material B is formed on the surface of the layer 2b, and a solid electrolyte layer 5 is sandwiched between the EC layers 3 and 4. The transparent substrate 1a / the transparent electrode layer 2a
/ EC layer 3 composed of EC material A / solid electrolyte layer 5 / EC
EC layer 4 made of material B / transparent electrode layer 2b / transparent substrate 1
This is a complementary element having a laminated structure b. And
The solid electrolyte layer 5 is formed of a proton conductive gel electrolyte.

The transparent substrates 1a and 1b are formed of a transparent glass material, plastic material, or organic-inorganic hybrid material. 1b is not particularly limited. When the transparent substrates 1a and 1b are formed of a plastic material or an organic-inorganic hybrid material, the element itself has flexibility and can be reduced in weight. The inorganic component of the organic-inorganic hybrid is, for example, S
iO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Nb
₂ O ₅ , a transition metal oxide such as Ta ₂ O ₅ , and the organic component is, for example, a polyolefin such as polyethylene (PE), polypropylene (PP), and polystyrene (PS);
Polyethers such as polyethylene oxide (PEO) and polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl formal (PVF), and polymethacrylic acid (P
MA), polymethyl methacrylate (PMMA), polyacrylate, vinyl chloride such as polyvinyl chloride (PVC), polyimide, polyamide, hydroxypropyl cellulose (HPC), cellulose such as methyl cellulose (MC), polycarbonate (PC ), Polyethylene terephthalate (PET), vinylidene, rubber-based materials, phenol, melanin, polyurethane and the like.

The transparent electrode layers 2a and 2b are made of ITO, SnO
₂ : F (fluorine-doped tin oxide), Ab-SnO ₂ (A
TO), ZnO, Al-ZnO (AZO), and the like, and a transparent substrate 1 by a generally known method such as a vacuum evaporation method or a sol-gel method.
It is formed by forming a film on a and 1b.

As EC materials for forming the EC layers 3 and 4, WO ₃ , V ₂ O ₅ , IrO _X , Prussian blue,
Polyaniline or the like is used, but an amorphous oxide is particularly preferable. For example, WO ₃ is used as the material A for forming the EC layer 3, and IrO ₂ .xH ₂ O (chemical formula is described as a hydrate as the EC material B for forming the EC layer 4, but is actually a hydroxide. May be used).

As a method for forming the EC layers 3 and 4, a gas phase method such as sputtering or CVD, or a liquid phase method such as a sol-gel method, a spray pyrolysis method or a hydrothermal method is used. In particular, it is preferable to form the EC layers 3 and 4 by forming a film by a sol-gel method using a metal salt or a metal alkoxide as a starting material.
Preferably, layers 3 and 4 are amorphous films. in this case,
Starting materials include WCl ₅ , WCl ₆ , W (O
R) ₅ , H ₂ WO ₄ , VOCl ₃ , VO (OR) ₃ , I
rCl ₃ , IrCl ₄ , etc. are used. R of the alkoxide is preferably an alkyl group having 1 to 5 carbon atoms. As a film forming method, a method such as spin, dip, flow, and bar coating is used. The heat treatment of the gel film is performed at, for example, 100 ° C. to 600 ° C.,
The reaction is preferably performed at a temperature of 400 ° C. or lower, more preferably 300 ° C. or lower. Within this temperature range, film formation on an organic-inorganic hybrid is possible.

As the proton conductive gel electrolyte forming the solid electrolyte layer 5, a substance containing one or more elements selected from the group consisting of carbon, oxygen, silicon, sulfur, phosphorus and hydrogen is used. . More specifically, it has a polyethylene glycol (PEG) chain and contains a hydrolyzate or hydrolyzed polycondensate (silicic acid or polysilicic acid or a derivative thereof) of an alkoxysilane,
Substances containing sulfate or phosphate groups are preferred. The solid electrolyte layer 5 is preferably formed by a sol-gel method using a metal salt or metal alkoxide as a starting material, and is preferably an amorphous film. More specifically, the proton conductive gel electrolyte is synthesized by a reaction between a metal salt or metal alkoxide, an aminoalkyl polyethylene glycol, and sulfuric acid or phosphoric acid. Then, the obtained reactant is transferred to the EC layer 3 (or EC layer 3) formed on the transparent substrates 1a and 1b.
The solid electrolyte layer 5 is formed by applying the solution on the surface of the layer 4) or pouring it between the EC layers 3 and 4 and then gelling.

In the above-described embodiment, the transmission type display mode EC element has been described. However, the present invention is also applicable to a reflection type display mode EC element as schematically shown in FIG. The same can be applied. E shown in FIG.
As in the EC element shown in FIG. 1, the C element has a transparent electrode layer 2 on the opposing surfaces of a pair of transparent substrates 1a and 1b.
a and 2b, and the surface of one of the transparent electrode layers 2a has an EC
An EC layer 3 made of a material A and an EC layer 4 made of an EC material B are formed on the surface of the other transparent electrode layer 2b, and a solid electrolyte layer 6 is sandwiched between the EC layers 3 and 4. I have. In the EC element, a white background plate 7 is provided on the solid electrolyte layer 6.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to specific examples of a method for manufacturing an EC device.

[Synthesis of WO ₃ coating solution 1] After dissolving tungsten hexachloride in dehydrated ethanol, the solution
The mixture was stirred while being heated at a temperature of ° C for 24 hours. Thus, a ₃ % by weight ethanol coating solution was prepared as WO3.

[Synthesis 2 of WO ₃ coating solution] After dissolving pentaethoxytungsten in dehydrated ethanol, the solution was hydrolyzed with a 0.1 M hydrochloric acid-ethanol solution (H ₂ O / W = 1 mol). Thus, a ₃ % by weight ethanol coating solution was prepared as WO3.

[Synthesis 1 of V ₂ O ₅ coating solution] After vanadium oxychloride was dissolved in dehydrated ethanol, the solution was stirred while heating at a temperature of 50 ° C for 24 hours. In this way, a 3% by weight ethanol coating solution as V ₂ O ₅ was prepared.

[Synthesis 2 of V ₂ O ₅ Coating Solution 2] By dissolving triethoxyvanadyl in dehydrated ethanol, V
_A 3% by weight ethanol coating solution was prepared as ₂ O ₅ .

[Synthesis of IrO ₂ coating solution] After iridium tetrachloride was dissolved in dehydrated ethanol, acetic acid in a molar equivalent to Ir was added to the solution. Thus, a ₂ % by weight ethanol coating solution as IrO ₂ was prepared.

[Synthesis of Gel Electrolyte] Tetraethoxysilane (TEOS), water (H ₂ O / TEOS = 8 times mol) and α, ω-di (2-aminopropyl) polyethylene glycol (7 times by weight of TEOS) ) To obtain a clear solution, and then add 1 M sulfuric acid (H ₂ O / TEOS) to the clear solution.
= 70 mol). Ultrasonic irradiation was performed on the obtained mixture to promote defoaming and gelation, thereby obtaining a gel electrolyte.

[Preparation of EC Element] (Examples 1 to 9) After each of the EC materials A and B was formed using a dip coater on each of the substrates on which the ITO electrode films were adhered, heat treatment was performed. A gel electrolyte was sandwiched between a pair of substrates on which an EC layer was formed, to produce a 40 mm square EC element. Substrate used, EC materials A and B, heating temperature,
Table 1 summarizes the thickness of the EC layer and the presence or absence of crystallinity. “Crystallinity” in Table 1 is the result of examination by X-ray diffraction. “X” indicates an amorphous film and “O” indicates a crystalline film. In Example 9, an SiO ₂ / polyimide hybrid was used as a hybrid material for forming the substrate.

[0040]

[Table 1]

Table 2 summarizes the evaluation results of the EC devices obtained in Examples 1 to 9. In Table 2, “Transmittance” means arrival transmittance, and “Response Speed” indicates a time until reaching the arrival transmittance. FIG. 3 is a graph showing the relationship between the application time of a voltage of 3 V and the change in current density at the time of coloring and decoloring for the EC device obtained in Example 1.

[0042]

[Table 2]

The responsivity of the EC elements of Examples 1 to 9 was all 1 second or less. In addition, the EC devices (Examples 7 to 9) in which the substrate was formed using a plastic material or an organic-inorganic hybrid material had flexibility, and a change in transmittance in a curved state was confirmed. Further, the EC elements of Examples 1 to 9
No change in transmittance or responsiveness was observed even after repeated operation over 200 times.

Comparative Example 1 An Li-ion gel electrolyte was prepared using glycidoxypropyltrimethoxysilane, tetraethoxysilane, lithium perchlorate, tetra-n-propoxyzirconium and tetraethylene glycol as starting materials. Similar to the first embodiment described above, ITO electrode film using a dip coater on a glass substrate having deposited _WO 3 -1 (coating solution prepared above Synthesis 1 of WO ₃ coating solution]) and _IrO 2 ( After each of the coating solutions prepared in [Synthesis of IrO ₂ coating solution] described above was formed, 30
Heat treatment was performed at a temperature of 0 ° C., and an Li ion gel electrolyte was sandwiched between a pair of substrates on which an EC layer was formed, to produce an EC device.

As shown in the evaluation results in FIG. 3, the EC element of Comparative Example 1 required a coloring time of 100 seconds or more until the transmittance became 30%.

(Comparative Example 2) An EC device was manufactured in the same configuration as in Example 1 described above, using a propylene carbonate solution of lithium perchlorate as a liquid Li ion electrolyte.

As shown in the evaluation results in FIG. 3, the EC element of Comparative Example 2 required a coloring time of 15 seconds or more until the transmittance became 30%.

As described above, the EC devices obtained in Examples 1 to 9 of the present invention have much better responsiveness than those of the conventional type EC devices obtained in Comparative Examples 1 and 2. Coloring-decoloring change was possible with a response speed within seconds. Also,
EC elements manufactured using substrates made of plastic materials or organic-inorganic hybrid materials are different from EC elements using ordinary glass substrates, and the elements themselves are flexible and lighter. Therefore, application to various fields is expected.

[0049]

According to the first aspect of the present invention, there is provided an all-solid-state EC device using a solid electrolyte, which has a response speed of 1%.
An EC element having excellent responsiveness within seconds can be obtained.

According to the second aspect of the present invention, it is possible to obtain a complementary EC device having a high response speed with a response speed of 1 second or less.

In each of the third and fourth aspects of the present invention, a flexible and lightweight EC element can be obtained, and various applications such as a film type display which has not been conventionally provided are expected. Further, in the invention according to claim 3, since a heating process is possible, the characteristics of the transparent electrode and the EC material can be improved, and a high-performance EC element can be provided.

According to the fifth aspect of the present invention, it is possible to obtain an all-solid-state EC device having an excellent response with a response speed within 1 second.

According to the sixth aspect of the present invention, when heat treatment is required when forming the EC layer, the heating temperature may be low, and the substrate is formed of a plastic material or an organic-inorganic hybrid material. EC using
An element can be manufactured.

In the invention according to claim 7, the heating temperature in forming the EC layer and the electrolyte layer by the sol-gel method can be low, and the substrate is formed of a plastic material or an organic-inorganic hybrid material. An EC element can be manufactured using a substrate.

According to the eighth aspect of the present invention, an EC device having an appropriate color density when a voltage is applied can be obtained.

According to the ninth aspect of the present invention, an all-solid-state EC device having an excellent response with a response speed of 1 second or less can be obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view schematically showing a basic configuration of an EC device, showing an example of an embodiment of the present invention.

FIG. 2 shows another embodiment of the present invention, and is a longitudinal sectional view schematically showing a basic configuration of an EC element.

FIG. 3 is a graph showing a relationship between an application time of a voltage of 3 V and a change in current density at the time of coloring and decoloring for an EC device obtained in an example of the present invention.

FIG. 4 is a schematic view showing a stacked structure of the EC element for explaining the reason why the EC element according to the present invention has a high response speed, and is a view showing a state where no voltage is applied to the EC element.

FIG. 5 is a schematic diagram showing a state when a voltage is applied to an EC element.

FIG. 6 is a longitudinal sectional view schematically showing one example of a basic configuration of a conventional EC element.

7 is a longitudinal sectional view schematically showing one example of a basic configuration of a conventional EC device of a type different from the EC device shown in FIG. 6;

[Explanation of symbols]

 1a, 1b Transparent substrate 2a, 2b Transparent electrode layer 3, 4 EC layer 5, 6 Solid electrolyte layer 7 White background plate

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2K001 AA02 CA02 CA04 CA08 CA19 CA20 CA37 DA04 DA19 5G301 CA30 CD01

Claims (9)

[Claims] 1. An electrochromic device in which an electrode layer is formed on each of opposing surfaces of a pair of substrates, and an electrochromic layer and a solid electrolyte layer are sandwiched between the two electrode layers. An electrochromic device formed of an electrolyte and having a response speed of 1 second or less. 2. Each of the substrates is formed of a transparent material, each of the electrode layers is formed of a transparent conductive material, and a solid electrolyte layer is provided between the first electrochromic layer and the second electrochromic layer. The electrochromic device according to claim 1, further comprising: 3. The electrochromic device according to claim 1, wherein each substrate is formed of an organic-inorganic hybrid material and has flexibility. 4. The electrochromic device according to claim 1, wherein each substrate is formed of a plastic material and has flexibility. 5. The proton conductive gel electrolyte forming the solid electrolyte layer is a substance containing one or more elements selected from the group consisting of carbon, oxygen, silicon, sulfur, phosphorus and hydrogen. The electrochromic device according to any one of claims 1 to 4. 6. The electrochromic device according to claim 1, wherein the electrochromic layer is an amorphous film. 7. An electrochromic layer and a solid electrolyte layer formed of a proton-conductive gel electrolyte are each composed of a metal alkoxide or a metal salt.
7. The electrochromic device according to claim 1, wherein the electrochromic device is an amorphous film formed by a gel method. 8. The electrochromic layer has a thickness of 50 μm.
The electrochromic device according to any one of claims 1 to 7, wherein the thickness is from m to 1 µm. 9. The proton conductive gel electrolyte forming the solid electrolyte layer is a substance having a polyethylene glycol chain, containing a hydrolyzate or hydrolyzed polycondensate of alkoxysilane and containing a sulfate group or a phosphate group. An electrochromic device according to any one of claims 1 to 8.