JP4051446B2 - Electrochromic device - Google Patents

Description

  The present invention relates to an electrochromic device using manganese oxide as an electrochromic material.

  In an electrochromic material, the absorbance changes due to an electrochemical change in the valence of a metal ion, so that a colored state and a decolored state can be reversibly selected. Utilizing this effect, electrochromic devices such as displays, filters, smart windows, anti-glare mirrors, and storage devices are realized. In general, electric chromic materials have attractive features such as low voltage / low power operation and memory characteristics, but it is difficult to develop materials that have both high absorbance change rate and high reliability. Due to the problems, few devices have been put into practical use except for electrochromic devices using tungsten oxide exhibiting reduced coloring.

  In particular, when an electrochromic material exhibiting oxidation colorability is combined with tungsten oxide exhibiting reduction colorability, a greater change in absorbance can be obtained, so that a complementary electrochromic device having excellent coloration efficiency can be achieved. For this reason, the development of an oxidation coloring electrochromic material having a large absorbance change rate and high reliability has been strongly desired. Manganese oxide has attracted attention as such a material, but it has been difficult to achieve both the rate of change in absorbance and reliability.

For example, a long-life thin film that can be discolored 10,000 times with manganese dioxide formed by electrolytic deposition has been reported (Non-patent Document 1), but its rate of change in absorbance is small, and practical electrolysis has been reported. It was not a chromic device. In addition, spinel-type manganese oxide Li _x Mn ₂ O ₄ (0 ≦ x ≦ 1) shows a large change in absorbance because it is accompanied by trivalent / tetravalent oxidation-reduction of manganese by Li ion extraction / insertion reaction. When the cathode is biased and becomes trivalent, there has been a problem that it is difficult to obtain high structural reliability because a phase transition from cubic to tetragonal crystal caused by Yang-Teller distortion occurs.

In addition, the layered manganese oxide is a material that is expected to facilitate the extraction / insertion reaction of alkali metal ions because of the large interlayer distance. However, this also has a drawback that Mn ₃ O ₄ is formed because the reduction of the manganese oxide proceeds too much when biased to the cathode, so that it cannot be oxidized electrochemically.
Surface Technology, Vol. 40, No. 7 (issued in 1989), pages 840-844

  The present invention has been made on the premise of the prior art described above, and in designing an electrochromic device, the colored state and the decolored state can be chemically controlled, that is, a high rate of change in absorbance. In addition, there is a demand for a highly reliable chromic material that can be used repeatedly, and it has been difficult to obtain such a chromic material. The present invention is basically intended to solve this material problem and thereby provide an excellent electrochromic device.

Therefore, as a result of diligent research in the inventors, as a chromic material, an oxide obtained by alternately laminating manganese oxide nanosheets and a polymer, which was developed by the inventors and applied for a patent earlier. When an ultra-thin manganese nanosheet (see Patent Document 1) is used, this ultrathin manganese oxide nanosheet is extremely excellent as a chromic material, that is, the colored state and the decolored state can be easily controlled chemically. It showed a high rate of change in absorbance, and was found to be highly reproducible and reliable.

Japanese Patent Application No. 2002-142285

This invention is made | formed based on the said knowledge, The structure is the following (1)-
(4) As described.
(1) A manganese oxide nanosheet including a first electrode, a second electrode, an electrolyte medium, and a circuit for applying a potential between the first electrode and the second electrode. And an ultra-thin film in which the polymer is alternately laminated, and the electrolyte medium is in contact with both the ultra-thin film in which the manganese oxide nanosheet and the polymer are alternately laminated and the second electrode. Chromic device.
(2) having a first electrode, a second electrode, an electrolyte medium, and a circuit for applying a potential between the first electrode and the second electrode, and manganese oxide on the first electrode An ultra-thin film in which nanosheets and polymers are alternately stacked is installed, and a reduced colored film selected from the group of tungsten oxide, molybdenum oxide, and a mixed oxide of tungsten oxide and molybdenum oxide is installed on the second electrode, and the electrolyte A complementary electrochromic device, wherein the medium is in contact with both an ultrathin film in which manganese oxide nanosheets and polymers are alternately laminated and a reduced colored film.
(3) The ultrathin film setting means in which the manganese oxide nanosheets and the polymer are alternately laminated includes a colloidal solution in which a layered manganese oxide raw material is peeled and dispersed, polydiallyldimethylammonium chloride (PDDA), polyethyleneimine By alternately immersing the first electrode in an aqueous solution containing one or two or more polymers selected from the group consisting of (PEI) and polyallylamine hydrochloride (PAH), the manganese oxide nanosheets and the polymer alternately The electrochromic device according to any one of (1) to (2) above, wherein the laminated ultrathin film is formed on the first electrode.
(4) From the group in which the electrolyte medium is composed of an alkali metal salt containing Li, K, Na, Rb, and Cs, an alkaline earth metal salt containing Mg and Ca, a quaternary ammonium salt, and a cyclic quaternary ammonium salt. The electrochromic device according to (1) or (2) above, which contains one or more selected salts.

  The manganese oxide nanosheet ultra-thin film used in the present invention has a large rate of change in absorbance, high reliability, and sufficient characteristics as a chromic material free from uneven coloring and decoloration, and the effects thereof will be described later. However, by adopting this ultra-thin film as an oxidative coloring film, it is possible to realize an electronic device such as a high-performance and highly reliable display, filter, smart window, anti-glare mirror, and storage device.

  The film thickness of this ultra-thin film is determined by the number of repetitions of the operation of alternately immersing the substrate in a colloidal solution and a cationic polymer solution in which manganese oxide nanosheets are suspended, and the ultra-thin film is completely uniform even on a large-area substrate. Another characteristic is that it is formed with a film thickness distribution. Compared to a conventional thin film formed by a film forming method such as a sputtering method, a film having excellent uniformity can be obtained, and further, a film having a uniform film thickness can be formed even on an uneven substrate surface. Formation of a uniform film thickness on such a substrate is one of the great advantages because it has been extremely difficult to form by the conventional sputtering method.

In addition, this manganese oxide nanosheet ultra-thin film exhibits a large absorbance in the ultraviolet-visible region even at a film thickness of 10 nm or less, and has an excellent function as an excellent electrochromic material with a large absorbance change rate and high reliability. An electrochromic device having a number of excellent features listed in the above is provided.
That is, 1) it is possible to form a uniform film thickness over a large area, so that an electrochromic device having a large area and no color unevenness can be provided. 2) A tungsten oxide thin film that is a conventional typical electrochromic material. In order to obtain practical coloration, a film thickness of 200 nm was necessary, but practical coloration was obtained with a film thickness of 1/20. An electrochromic device can be provided. 3) Since a film can be formed with a uniform film thickness on a substrate having a convex lens-like surface shape, an electrochromic display device having a large viewing angle can be provided.

  Here, the manganese oxide employed in the electrochromic device of the present invention is an ultra-thin body in which manganese oxide nanosheets and polymers are alternately laminated, and it has been developed by the present inventors as described above. Just as you did. In the manufacturing process, the nanosheet and the polymer are adsorbed on the substrate by repeating the operation of alternately immersing the substrate in the colloidal solution and the cationic polymer solution in which the manganese oxide nanosheets are suspended. It is formed by laminating films that are alternately repeated at intervals of nm level (see Patent Document 1). The present inventors have further examined the electrochromic characteristics of the ultrathin film formed by this process, and found that the ultrathin film has a large absorbance change rate and high reliability. The preparation of the ultrathin film used in the present invention and its electrochromic characteristics will be described in detail below.

  First, a glass substrate coated with indium-tin oxide (referred to as an ITO glass substrate) is prepared, and this glass substrate is alternately immersed in a colloidal solution and a cationic polymer solution in which manganese oxide nanosheets are suspended. By repeating the process repeatedly, the nanosheet and the polymer were adsorbed on the substrate, respectively, and an ultrathin film having a thickness of 9.3 nm in which the manganese oxide nanosheet and the polymer were alternately laminated was formed on the ITO glass substrate. The film thickness was determined from the X-ray diffraction peak angle from the laminated structure. As a result, it became clear that the lamination period was deposited with a thickness of 0.93 nm accurately in the film thickness direction.

FIG. 1 shows a cyclic voltammogram when the ITO glass substrate on which the ultrathin film is deposited is used as a working electrode and silver is used as a reference electrode. The solution contains 0.1 mold ^-3 lithium perchlorate and the counter electrode is platinum. The vertical axis represents the current density at the working electrode when the potential of the working electrode with respect to the reference electrode was changed between −1.5 V and +1.0 V at a sweep rate of 20 mVs ⁻¹ .

  As a result, the peak where the current value is maximum in the forward direction corresponds to an increase reaction of manganese valence due to oxidation, and the valley where the current is minimum in the reverse direction corresponds to a decrease reaction of manganese valence due to reduction. It became clear to do. The valence of manganese in the ultrathin film before the potential sweep was determined to be 3.87 from the titration method. The working electrode potential with respect to the reference electrode at this time was 0.218 V. From the fact that there is one peak and one valley and its shape, it is clear that the valence change is 1, so the valence of manganese is predicted to be trivalent on the negative potential side and tetravalent on the positive potential side. Is done.

  FIGS. 2A and 2B are ultraviolet-visible absorption spectra of the working electrode when the working electrode potential is −1.5 V and +1.0 V, respectively. It can be seen that the absorbance is large and colored at +1.0 V against −1.5 V. In general, the intensity of an absorption spectrum varies depending on the thickness of a thin film used for measurement. Therefore, the nonuniformity of the film thickness appears as the nonuniformity of the absorption intensity. The ultra-thin film used in the present invention has perfect thickness uniformity, and therefore does not have non-uniform absorption intensity. For this reason, the ultra-thin film used in the present invention exhibited excellent electrochromic characteristics such as no coloring unevenness and decoloring unevenness, which was a defect of conventional electrochromic materials.

FIG. 3 shows the dependency of the absorbance at a wavelength of 404 nm on the working electrode potential. FIG. 4 shows the change in electric potential on the horizontal axis in FIG. 3 converted to the change in charge amount using the result of the cyclic voltammogram in FIG. It can be seen that the absorbance changes almost linearly with the amount of charge. From the slope of FIG. 4, the absorbance change rate was determined to be 54.8 cm ² C ⁻¹ . This value is the largest value for manganese oxide.

  It is thought that the valence of manganese changes linearly with the amount of charge. If the value of the working electrode potential 0.218V before the potential sweep determined from the linear dependence and the titration method is 3.87V, it is extrapolated from FIG. 4 to -1.5V and + 1.0V. The valence can be accurately determined. The determined valence was trivalent at -1.5V and tetravalent at + 1.0V. Therefore, it is considered that all manganese ions in the ultrathin film are stored in the redox reaction.

  The cyclic voltammogram was repeatedly measured, and the absorbance change rate at that time was examined. The absorbance change rate did not deteriorate after 10,000 repetitions. Moreover, the structure of the ultrathin film after 10,000 iterations was analyzed by X-ray diffraction, but no structural change was observed. Thus, the present invention revealed that the ultrathin film in which the manganese oxide nanosheets and the polymer are alternately laminated has both a large absorbance change rate and high reliability.

  The large rate of change in absorbance is obtained by the structure in which manganese oxide nanosheets and polymers are alternately laminated, so that lithium ions can be easily inserted and desorbed to induce electrochromism. This is because the diffusion coefficient of lithium ions therein is large and the thickness of the polymer layer is sufficiently thin at a sub-nm to nm level, so that the diffused lithium ions can efficiently reduce manganese.

Furthermore, the high reliability can be obtained, since the inter-manganese oxide nanosheets is filled polymers, MnO ₆ eight manganese lithium ions are inserted into the ultra-thin film be reduced, which constitutes the manganese oxide nanosheets This is because structural changes of the face pieces are suppressed. As a result, the reliability is not impaired even by repeated coloring and decoloring.

  A first embodiment of an electrochromic device according to the present invention is an oxidation-colored electrochromic device having, as an oxidation-colored layer, an ultra-thin film in which manganese oxide nanosheets and polymers are alternately laminated, and has the configuration described in (1) above. The second mode is a complementary electrochromic device, characterized in that it has the configuration described in (2) above.

Here, the ultrathin film in which manganese oxide nanosheets and polymers are alternately laminated has a structure disclosed in Patent Document 1. Specifically, one or two selected from the group consisting of manganese oxide nanosheets whose two-dimensional crystallites are represented by MnO ₂ , polydiallyldimethylammonium chloride (PDDA), polyethyleneimine (PEI), and polyallylamine hydrochloride (PAH). Both components of the polymer of the seed or more have a structure in which they are alternately stacked at intervals of sub nm to nm level. As described above, when the ultrathin film is formed by alternately laminating the manganese oxide nanosheets and the polymer on the first electrode, the film thickness is determined by the number of laminations, and the ultrathin film It is formed with a completely uniform film thickness distribution on the electrode. In addition, the ultrathin film is formed with a uniform film thickness on an uneven surface. Therefore, an electrochromic device without uneven coloring and decoloring and an electrochromic device with a large viewing angle formed on a surface having a shape on a convex lens are provided.

The optimum thickness of the ultrathin film for obtaining a large dynamic range absorbance change between coloring and decoloring is 5 nm or more and 30 nm or less. If it is less than 5 nm, sufficient coloring cannot be obtained, and if it exceeds 30 nm, sufficient decoloring cannot be obtained. However, in an electrochromic device that does not require a large dynamic range, an ultra-thin film having a film thickness outside the above range is also used.

  The first electrode may be a transparent conductor or an opaque conductor. In the case where the first electrode is provided on the first substrate, the first substrate may be transparent or opaque. That is, when the electrochromic device is a smart window or a filter, the first electrode is a transparent conductor disposed on a transparent first substrate. When the electrochromic device is an anti-glare mirror or display, even if the electrochromic device is a transparent or opaque conductor placed on the opaque first substrate, it is transparent or opaque placed on the transparent first substrate. It may be a conductor. When the electrochromic device is a multilayer optical disk type storage device, the first electrode is a transparent conductor.

  Therefore, the first electrode is a transparent conductor or an opaque conductor placed on a known transparent first substrate such as glass or epoxy resin, or a known opaque first substrate such as semiconductor or metal. It is. The transparent conductor is selected from the group consisting of indium-tin oxide and fluorine-doped tin oxide. The opaque conductor is selected from the group consisting of platinum, gold, aluminum, iron, nickel, tungsten, titanium, molybdenum, and polysilicon doped with impurities at a high concentration. It may be a body.

  When the reduction coloring film is not provided on the second electrode, the electrolyte medium is disposed in a configuration in which both the ultrathin film in which the manganese oxide nanosheets and the polymer are alternately stacked and the second electrode are in contact with each other. The chromic device functions as an oxidation coloring type electrochromic device which is the first form of the electrochromic device according to the present invention.

  When a reduced colored film is provided on the second electrode, the electrolyte medium is disposed in a configuration in which both the ultrathin film in which manganese oxide nanosheets and polymers are alternately laminated and the reduced colored film are in contact with each other. The chromic device functions as a complementary electrochromic device which is the second form of the electrochromic device according to the present invention. That is, when the first electrode is biased to a positive potential with respect to the second electrode, both the oxidized colored film and the reduced colored film are colored, and when biased to a negative potential, both films are decolored.

  The reducing coloring film is made of an inorganic thin film selected from the group consisting of tungsten oxide, molybdenum oxide, and a mixed oxide of tungsten oxide and molybdenum oxide. The reducing colored film may be an organic thin film selected from a conductive polymer compound group consisting of polyaniline, polythiophene, polypyrrole, polybenzidine, and polyisoanaphthene.

  Complementary and oxidation-colored electrochromic cell applications, that is, a second electrode and a second electrode are installed according to the operation of a smart window, a filter, an antiglare mirror, a display, a storage device, etc. The substrate material is selected. Therefore, the second electrode is a transparent conductor or an opaque conductor placed on a known transparent second substrate such as glass or epoxy resin or a known opaque second substrate such as semiconductor or metal. It is. The transparent conductor is selected from the group consisting of indium-tin oxide and fluorine-doped tin oxide. The opaque conductor is selected from the group consisting of platinum, gold, aluminum, nickel, tungsten, titanium, molybdenum, polysilicon doped with impurities at a high concentration, but other known opaque conductors may also be used. Good.

The first substrate on which the first electrode is formed and the second substrate on which the second electrode is formed are the same as long as the first electrode and the second electrode are electrically insulated. Also good. In the case of configuring a complementary electrochromic device, the first substrate and the second substrate are usually separate and are disposed to be spatially opposed to each other. In this case, the electrolyte medium is disposed in a space sandwiched between two substrates. However, the first electrode and the second electrode can be arranged separately on the front and back surfaces of the same transparent substrate. When this arrangement is selected, an opening through which the electrolyte medium can pass can be provided in the transparent substrate for the purpose of avoiding a potential drop in the electrolyte medium.

  The electrolyte medium may be a liquid system or a gelled liquid system. As the liquid system, a solution obtained by dissolving a supporting electrolyte such as a salt, an acid, or an alkali in a solvent can be used. The liquid solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but preferably has polarity. Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, acetanilyl, γ-butyllactone, γ-valerolactone, tetraglyme, sulfolane, dimethylformamide, tetrahydrofuran, propiononitrile, glutaro It is selected from nitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidine, dioxolane, trimethyl phosphate, polyethylene glycol and the like. These can be used alone or as a mixture in use.

The salts as the supporting electrolyte are not particularly limited, and various alkali metal salts including Li, K, Na, Rb, and Cs, alkaline earth metal salts including Mg and Ca, quaternary ammonium salts, and cyclic quaternary salts. Examples thereof include ammonium salts, specifically, LiClO ₄ , LiSCN, Li
BF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiPF ₄ , LiI, NaI, NaSCN, Na
Alkali metal salts of Li, K, Na such as ClO ₄ , NaBF ₄ , NaAsF ₆ , KSCN, KCl, (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ BNF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , C ₂ H ₅
Preferred examples include quaternary ammonium salts such as ₄ NBr, C ₂ H ₅ ) ₄ NClO ₄ , (n-C ₄ H ₉ ) ₄ NClO ₄ and cyclic quaternary ammonium salts, or mixtures thereof.

  Acids as the supporting electrolyte are not particularly limited, and examples thereof include inorganic acids and organic acids. Specific examples include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids. The alkali as the supporting electrolyte is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  As the gelled liquid electrolyte medium, it is possible to use a gelled liquid medium containing a filler made of a polymer or inorganic particles or a gelling agent in the liquid electrolyte medium. . The polymer to be used is not particularly limited, and polyacrylonitrile, carboxymethyl cellulose, polyvinyl chloride, polyethylene oxide, polysilane, polycarbonate, polyvinyl acetate, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide. And Nafion. Examples of the filler made of inorganic particles include polysilane, silica, alumina, cerium oxide, and zinc oxide. The gelling agent is not particularly limited, and examples thereof include oxyethylene methacrylate, oxyethylene acrylate, urethane acrylate, acrylamide, and agar.

Examples Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples of ultrathin films, but the present invention is not limited to the following examples.

Example 1;
An ultrathin film 3 in which manganese oxide nanosheets and polymers were alternately laminated was formed on the first electrode 2 as follows. That is, first, 0.4 g of layered manganate H _0.13 MnO ₂ .0.7H ₂ O obtained by acid treatment of layered potassium manganate K _0.45 MnO ₂ was added to 100 cm ³ of tetrabutylammonium hydroxide solution at room temperature. After shaking for a week, a colloidal solution in which manganese oxide nanosheets were dispersed was obtained. This was diluted to a concentration of 0.08 g dm ⁻³ , and hydrochloric acid was further added to adjust the pH to 9. On the other hand, a 2% by weight polydiallyldimethylammonium (PDDA) chloride aqueous solution was prepared, and its pH was adjusted to 9. Next, a first electrode 2 made of an indium-tin oxide transparent conductive layer having a thickness of 0.4 μm is formed on one surface of the first substrate 1 which is a glass plate, and the other surface is covered with a photoresist film. After that, it was washed with a 2% solution of Mercan ExtraMA02 and Milli-Q pure water.

  Next, this first substrate was immersed in an aqueous polyethyleneimine solution having a concentration of 0.25% by weight for 20 minutes and sufficiently washed with Milli-Q pure water. The first substrate thus cleaned and pretreated was immersed in 1) the above manganese oxide nanosheet colloidal solution. 2) After 20 minutes, it was thoroughly washed with Milli-Q pure water and dried by blowing an argon stream. 3) Next, this substrate was immersed in a PDDA solution for 20 minutes. 4) Subsequently, the substrate was thoroughly washed with Milli-Q pure water. By repeating the above operations 1) to 4) 10 times, an ultrathin film 3 in which manganese oxide nanosheets having a thickness of 9.3 nm and polymers are alternately stacked is provided on the first substrate 1. 1 was synthesized on the electrode 2. Further, the glass film was exposed on the back surface of the first substrate by removing the photoresist film on the back surface. Thus, the 1st board | substrate with which the oxidation coloring film was formed was created.

  A 0.4 μm-thick indium-tin oxide transparent conductive layer to be the second electrode 5 is provided on one surface of the second substrate 4 made of a glass plate, and a 0.2 μm-thickness is further formed thereon. A reduction coloring film 6 made of tungsten oxide was formed by sputtering. Thus, the 2nd board | substrate with which the reduction coloring film | membrane was formed was produced.

Furthermore, as shown in FIG. 5, the first substrate and the second substrate are arranged so that the ultrathin film 3 in which the tungsten oxide layer 6, the manganese oxide nanosheet, and the polymer are alternately stacked faces each other, and the thickness is 0. After being sandwiched between 1 mm spacers 7 and bonded with an epoxy resin, a propylene carbonate solution containing 0.1 mol dm ⁻³ lithium perchlorate LiClO ₄ was injected as an electrolyte medium 8 into the gap.

  The intensity of transmitted light from the back surface of the second substrate when light having a wavelength of 404 nm is incident on the surface of the first substrate where the glass is exposed can be controlled by the potential of the first electrode with respect to the second electrode. it can. Compared to when the potential is set to -3V, the transmitted light intensity when set to + 3V is attenuated to 1/10. Although the potential application of -3V and + 3V was repeated 10,000 times, no deterioration of the transmitted light intensity control characteristic was observed, and a high-performance and highly reliable electrochromic filter was realized.

  Since the ultrathin film provided on the first electrode has a uniform film thickness, an electrochromic filter free from uneven coloring and decoloring was realized. In addition, since the film thickness of the ultrathin film is determined by the number of alternate immersions in the manganese oxide nanosheet colloid solution and the PDDA solution, there is a feature that an electrochromic filter having uniform characteristics can be formed with good reproducibility.

  Since the electrochromic device shown in this embodiment can attenuate ultraviolet rays by applying a potential, it goes without saying that it can be used not only as a filter but also as a smart window.

The present invention has the basic performance of high absorbance change rate and high reliability by selecting and using the manganese oxide nanosheet ultra-thin film previously filed by the inventor group as a chromic material. It is possible to design an electrochromic device with many features such as large size, economy, and compatibility with complex surface shape designs, and its significance is extremely large. In the future, considering that electrochromic devices are expected to be used and developed in various fields such as displays, smart windows, anti-glare mirrors, storage devices, etc., the technical field using these devices has begun. It is expected to contribute greatly to the development of industry widely.

It is a graph which shows the cyclic voltammogram of the ultra-thin film used for this invention. It is a graph which shows the ultraviolet visible absorption spectrum of the ultra-thin film used for this invention, (a) and (b) are spectra when a working electrode electric potential is -1.5V and + 1.0V, respectively. It is a graph which shows the working electrode electric potential dependence of the light absorbency in wavelength 404nm of the ultra-thin film used for this invention. It is a graph which shows the charge amount dependence of the light absorbency in wavelength 404nm of the ultra-thin film used for this invention. 3 is a cross-sectional view showing the structure of an electrochromic filter created according to Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; 1st board | substrate 2; 2 is 1st electrode 3; Ultrathin film 4 by which manganese oxide nanosheet and polymer were laminated | stacked alternately; 2nd board | substrate 5; 2nd electrode 6; Reductive coloring film | membrane 7; Sir 8; Electrolyte medium

Claims (4)

  A first electrode, a second electrode, an electrolyte medium, and a circuit for applying a potential between the first electrode and the second electrode, wherein the manganese oxide nanosheet and the polymer are on the first electrode. An oxidation-colored electrochromic device, wherein ultrathin films alternately stacked are provided, and an electrolyte medium contacts both the ultrathin films alternately stacked with manganese oxide nanosheets and polymers and the second electrode.   A first electrode; a second electrode; an electrolyte medium; and a circuit for applying a potential between the first electrode and the second electrode. A manganese oxide nanosheet and a polymer on the first electrode An ultra-thin film is alternately stacked, and a reduction coloring film selected from the group of tungsten oxide, molybdenum oxide, and a mixed oxide of tungsten oxide and molybdenum oxide is installed on the second electrode, and the electrolyte medium is oxidized. A complementary electrochromic device characterized by contacting both an ultrathin film and a reduced colored film in which manganese nanosheets and polymers are alternately laminated.   The ultra-thin film setting means in which the manganese oxide nanosheets and the polymer are alternately laminated includes a colloidal solution in which a layered manganese oxide raw material is peeled and dispersed, polydiallyldimethylammonium chloride (PDDA), polyethyleneimine (PEI) And manganese oxide nanosheets and polymers were alternately laminated by immersing the first electrodes alternately in an aqueous solution containing one or more polymers selected from the group consisting of polyallylamine hydrochloride (PAH) The electrochromic device according to claim 1, wherein an ultrathin film is formed on the first electrode. The electrolyte medium was selected from the group consisting of alkali metal salts containing Li, K, Na, Rb, Cs, alkaline earth metal salts containing Mg, Ca, quaternary ammonium salts, and cyclic quaternary ammonium salts. The electrochromic device according to claim 1, comprising at least one salt.