WO2024122611A1 - 黒色エレクトロクロミック材料およびその製造方法、塗料およびその製造方法、混合塗料およびその製造方法、色可変電極およびその製造方法およびエレクトロクロミック素子 - Google Patents

黒色エレクトロクロミック材料およびその製造方法、塗料およびその製造方法、混合塗料およびその製造方法、色可変電極およびその製造方法およびエレクトロクロミック素子 Download PDF

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WO2024122611A1
WO2024122611A1 PCT/JP2023/043811 JP2023043811W WO2024122611A1 WO 2024122611 A1 WO2024122611 A1 WO 2024122611A1 JP 2023043811 W JP2023043811 W JP 2023043811W WO 2024122611 A1 WO2024122611 A1 WO 2024122611A1
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Prior art keywords
paint
black
electrochromic
color
nanoparticles
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English (en)
French (fr)
Japanese (ja)
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一樹 田嶌
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National Institute of Advanced Industrial Science and Technology AIST
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National Institute of Advanced Industrial Science and Technology AIST
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Priority to EP23900723.0A priority Critical patent/EP4632035A1/en
Priority to JP2024562992A priority patent/JPWO2024122611A1/ja
Publication of WO2024122611A1 publication Critical patent/WO2024122611A1/ja
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

Definitions

  • the present invention relates to a black electrochromic material and its manufacturing method, a paint and its manufacturing method, a mixed paint and its manufacturing method, a color-changeable electrode and its manufacturing method, and an electrochromic element.
  • An electrochromic device is a color-changeable device that uses an electrochromic material (EC material) that changes color through electrochemical oxidation and reduction. It is used in car mirrors to control reflectance by changing color, and in car and building windows to control the transmittance of solar radiation and infrared rays and improve air conditioning efficiency. It is also being considered for use in displays, sunglasses, and other applications.
  • ECDs electrochromic material
  • applications of ECDs to light-control glass for building materials and vehicles have been actively considered.
  • the color is extremely important. In particular, it is desirable to realize colors such as black, gray, and brown.
  • many of the ECDs currently on the market exhibit a color change from blue to transparent.
  • ECDs Materials used in these ECDs include oxides such as tungsten oxide (Patent Document 1), small molecules such as viologen (Patent Document 2), polymers such as PEDOT-PSS (Patent Document 3), and coordination polymers such as metal cyano complexes (Patent Document 4).
  • oxides such as tungsten oxide (Patent Document 1), small molecules such as viologen (Patent Document 2), polymers such as PEDOT-PSS (Patent Document 3), and coordination polymers such as metal cyano complexes (Patent Document 4).
  • tungsten oxide Patent Document 1
  • small molecules such as viologen
  • Patent Document 3 polymers
  • coordination polymers such as metal cyano complexes
  • Patent Document 5 Non-Patent Documents 1 to 3
  • organic polymer materials generally have problems with light resistance, and are not suitable for use in light-control glass.
  • inorganic materials are thought to have a certain advantage.
  • metal oxides and metal cyano complexes have already been commercialized.
  • the material For light-control glass applications, it is required that the material not only has a certain color when colored, but also becomes colorless and transparent when decolorized. Furthermore, to prevent scattering, it is necessary to form a smooth thin film on the transparent electrode.
  • no inorganic black-transparent electrochromic materials have been reported at present.
  • an inorganic electrochromic material that exhibits a reversible color change between black and transparent, and a manufacturing method thereof.
  • a paint mixed paint that contains such an electrochromic material, a manufacturing method thereof, a color-changeable electrode, and an electrochromic element.
  • the present invention has been made in consideration of the above circumstances, and aims to provide an electrochromic material that exhibits a reversible color change between black and transparent and a manufacturing method thereof, a paint and mixed paint that contain an electrochromic material and exhibits a reversible color change between black and transparent and a manufacturing method thereof, a color-changeable electrode, and an electrochromic element.
  • a black electrochromic material that reversibly changes color between black and transparent through an electrochemical oxidation-reduction reaction A black electrochromic material comprising one or more types of nanoparticles selected from the group consisting of copper oxide nanoparticles, which are a product of heat treatment of basic copper carbonate, titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, and metallic iridium nanoparticles.
  • a paint that reversibly changes color between black and transparent by an electrochemical oxidation-reduction reaction A paint comprising the black electrochromic material according to [1] dispersed in a weakly acidic solvent.
  • Zeta potential is -36 to -28 mV The paint according to any one of [2] to [4] above.
  • a mixed paint comprising any one of the paints according to [2] to [5] above and a paint containing another oxide-based electrochromic material.
  • the binder includes one or more selected from polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), polyethylene glycol, polypropylene glycol, trifluoromethanesulfonylimide, methacrylic acid methyl ester, and polydimethylsiloxane; Any of the paints described in [2] to [5] above or the mixed paint described in [6] above.
  • PVA polyvinyl alcohol
  • CMC sodium carboxymethylcellulose
  • HPC hydroxypropyl cellulose
  • HEC hydroxyethyl cellulose
  • polyethylene glycol polypropylene glycol
  • trifluoromethanesulfonylimide methacrylic acid methyl ester
  • polydimethylsiloxane any of the paints
  • a color-changeable electrode comprising a thin film containing a black electrochromic material formed on an electrode layer using any one of the paints [2] to [5] or the mixed paint [6].
  • An electrochromic element comprising the color-changeable electrode according to [8].
  • a method for producing a black electrochromic material that reversibly changes color between black and transparent by an electrochemical oxidation-reduction reaction comprising the steps of: A method for producing a black electrochromic material, comprising a first step of heating basic copper carbonate to obtain copper oxide nanoparticles.
  • a method for producing a paint that reversibly changes color between black and transparent by an electrochemical oxidation-reduction reaction comprising the steps of: The following steps: A first step of heating basic copper carbonate to obtain copper oxide nanoparticles; and A method for producing a paint, comprising a second step of dispersing the copper oxide nanoparticles in a weakly acidic solvent to obtain a paint.
  • a method for producing a paint according to [12] characterized in that in the second step, the solvent contains citric acid and has a pH of 3.0 or less.
  • a method for producing a mixed coating material comprising a step of mixing the coating material according to any one of [2] to [5] above with a coating material containing another oxide-based electrochromic material.
  • a method for producing a coating material or a mixed coating material comprising using, as a binder, one or more selected from polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), polyethylene glycol, polypropylene glycol, trifluoromethanesulfonylimide, methyl methacrylate, and polydimethylsiloxane.
  • a method for producing a color-changeable electrode comprising the step of forming a thin film containing a black electrochromic material on an electrode layer using any one of the paints [2] to [5] above or the mixed paint [6] above.
  • a method for producing an electrochromic element comprising the step of laminating the color-changeable electrode of [7] above and an electrolyte layer.
  • Photograph of copper oxide nanoparticles obtained from basic copper carbonate. 1 is a photograph showing the appearance of a paint in which copper oxide nanoparticles are dispersed (a paint of the present invention).
  • FIG. 1 shows optical transmission spectra of black paints in which oxide nanoparticles are dispersed at various solid amounts.
  • FIG. 1 is a diagram showing the chromaticity of black paints in which oxide nanoparticles are dispersed at various solid amounts.
  • FIG. 1 is a structural schematic diagram showing an example of an electrode made from a paint in which copper oxide nanoparticles are dispersed.
  • FIG. 1 is a structural schematic diagram showing an example of an electrochromic element.
  • FIG. 1 shows the results of X-ray structural analysis of copper oxide nanoparticles.
  • FIG. 1 is a photograph showing the appearance of the paint of the present invention, showing its pH dependency.
  • FIG. 2 is a graph showing the particle size distribution of the coating material of the present invention.
  • 1 is a diagram showing a CV curve of a thin-film electrode made from a paint (paint of the present invention) in which copper oxide nanoparticles with a solid content of 5 wt. % are dispersed.
  • FIG. 1 shows the results of X-ray structural analysis of copper oxide nanoparticles extracted from the coating material of the present invention to which PVA has been added.
  • FIG. 2 shows the average particle size of the paint of the present invention with added PVA.
  • FIG. 1 shows the zeta potential of a paint of the present invention with added PVA.
  • FIG. 1 shows a surface FE-SEM image of a thin-film electrode made from the coating material of the present invention to which PVA has been added.
  • 1 is a graph showing the electrochromic properties of a thin film electrode made from a coating material of the present invention with added PVA.
  • FIG. 13 is a diagram showing the change in optical transmission spectrum of a thin-film electrode produced using the coating material of the present invention.
  • 1 is a photograph showing the appearance of a thin-film electrode produced using the coating material of the present invention.
  • FIG. 1 is a diagram showing changes in the optical transmission spectrum of a thin-film electrode prepared from a paint of the present invention (copper oxide nanoparticle dispersion paint) and a tungsten oxide dispersion paint.
  • FIG. 1 shows particle size distributions of paints of the present invention (titanium oxide nanoparticle dispersion paint, titanium nitride nanoparticle dispersion paint, metallic iridium nanoparticle dispersion paint, nickel hydroxide nanoparticle dispersion paint, copper oxide nanoparticle dispersion paint, and tungsten oxide nanoparticle dispersion paint).
  • FIG. 1 is a photograph showing the appearance of a thin-film electrode produced using the paint of the present invention (a paint having a titanium oxide nanoparticle dispersion, a paint having a titanium nitride nanoparticle dispersion, a paint having a metallic iridium nanoparticle dispersion, a paint having a nickel hydroxide nanoparticle dispersion, a paint having a copper oxide nanoparticle dispersion, and a paint having a tungsten oxide nanoparticle dispersion).
  • a paint having a titanium oxide nanoparticle dispersion a paint having a titanium nitride nanoparticle dispersion, a paint having a metallic iridium nanoparticle dispersion, a paint having a nickel hydroxide nanoparticle dispersion, a paint having a copper oxide nanoparticle dispersion, and a paint having a tungsten oxide nanoparticle dispersion.
  • FIG. 1 shows changes in the optical transmission spectra of thin-film electrodes made from the paints of the present invention (titanium oxide nanoparticle dispersion paint, titanium nitride nanoparticle dispersion paint, metal iridium nanoparticle dispersion paint, nickel hydroxide nanoparticle dispersion paint, copper oxide nanoparticle dispersion paint, and tungsten oxide nanoparticle dispersion paint).
  • FIG. 1 shows changes in the optical transmission spectra of thin-film electrodes made from the paints of the present invention (titanium oxide nanoparticle dispersion paint, titanium nitride nanoparticle dispersion paint, metal iridium nanoparticle dispersion paint, nickel hydroxide nanoparticle dispersion paint, copper oxide nanoparticle dispersion paint, and tungsten oxide nanoparticle dispersion paint).
  • FIG. 1 is a diagram summarizing the change in chromaticity accompanying the electrochemical oxidation-reduction reaction of thin-film electrodes made from the paints of the present invention (titanium oxide nanoparticle dispersion paint, titanium nitride nanoparticle dispersion paint, metallic iridium nanoparticle dispersion paint, nickel hydroxide nanoparticle dispersion paint, copper oxide nanoparticle dispersion paint, and tungsten oxide nanoparticle dispersion paint).
  • titanium oxide nanoparticle dispersion paint titanium nitride nanoparticle dispersion paint
  • metallic iridium nanoparticle dispersion paint metallic iridium nanoparticle dispersion paint
  • nickel hydroxide nanoparticle dispersion paint nickel hydroxide nanoparticle dispersion paint
  • copper oxide nanoparticle dispersion paint and tungsten oxide nanoparticle dispersion paint.
  • FIG. 1 shows the time change in the optical transmission spectrum of thin-film electrodes made from the paints of the present invention (titanium oxide nanoparticle dispersion paint, titanium nitride nanoparticle dispersion paint, metal iridium nanoparticle dispersion paint, nickel hydroxide nanoparticle dispersion paint, copper oxide nanoparticle dispersion paint, and tungsten oxide nanoparticle dispersion paint).
  • FIG. 2 is a diagram showing the particle size distribution of the paint of the present invention (zirconium oxide nanoparticle dispersed paint).
  • FIG. 1 is a diagram showing the optical transmission spectrum of a thin-film electrode made from the paint of the present invention (zirconium oxide nanoparticle dispersed paint).
  • the inventors discovered that it is possible to obtain copper oxide nanoparticles (electrochromic material) that stably exhibit a color change from black to transparent by simply firing the material in a furnace using basic copper carbonate as a raw material, and thus completed the present invention.
  • the inventors also discovered that it is possible to produce a black color with various oxide materials (e.g., titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, metallic iridium nanoparticles, etc.) by controlling their particle size and functionality, and that they can be used as black electrochromic materials.
  • various oxide materials e.g., titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, metallic iridium nanoparticles, etc.
  • the following describes one embodiment of the black electrochromic material, paint, and mixed paint of the present invention, their manufacturing methods, the color-changeable electrode and its manufacturing method, and the electrochromic element.
  • the black electrochromic material (EC material) of the present invention can be used in paints that undergo a reversible color change between black and transparent due to an electrochemical oxidation-reduction reaction.
  • transparent does not necessarily mean that the absorption coefficient in the visible light region is 0. What is important is that there is a sufficient difference between the absorbance when colored and the absorbance when colorless and transparent, and the ratio of the absorbance when colored to the absorbance when colorless and transparent is preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more in the wavelength range of 450 nm to 550 nm where human visibility is high.
  • one embodiment of the black electrochromic material of the present invention contains copper oxide nanoparticles that are a heat-treated product of basic copper carbonate.
  • the basic copper carbonate referred to here is a general term for basic salts of copper (II) carbonate, and is an inorganic copper salt consisting of divalent copper ions Cu2 + , carbonate ions CO32- , and hydroxide ions OH- .
  • the method for producing the black electrochromic material of the present invention also includes a first step of heating basic copper carbonate to obtain copper oxide nanoparticles.
  • copper oxide nanoparticles refers to nanoparticles synthesized from basic copper carbonate, whose composition is represented by CuOx.
  • copper oxide nanoparticles can be synthesized as a black electrochromic material (EC material) by heating basic copper carbonate as a raw material according to the following reaction formula.
  • EC material black electrochromic material
  • a paint copper oxide nanoparticle dispersed paint
  • Basic copper carbonates have different ratios of carbonate ions and hydroxide ions, and known examples include Cu 2 (OH) 2 CO 3 , CuCO 3.Cu (OH) 2 , 2CuCO 3.Cu (OH) 2 , and Cu 2 (OH) 2 CO 3.H 2 O.
  • a general basic copper carbonate reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • copper oxide nanoparticles can be obtained according to the following reaction formula.
  • copper oxide nanoparticles can be synthesized by heating basic copper carbonate as a raw material in air in an electric furnace.
  • heating temperature or heating time There are no particular limitations on the heating temperature or heating time, but for example, by heating basic copper carbonate in an electric furnace at 250 to 500°C for about 1 to 10 hours, copper oxide nanoparticles in the form shown in Figure 1 can be obtained.
  • the particle size (average particle size) of the copper oxide nanoparticles is preferably small in order to improve the electrochemical response speed (to increase the specific surface area), and is also preferably small in order to form a smooth thin film.
  • the particle size (average particle size) means the particle size at 50% of the cumulative value in the particle size distribution obtained by a laser diffraction/scattering method or the like.
  • the upper limit of the primary particle size of the copper oxide nanoparticles is preferably 500 nm or less, more preferably 300 nm or less, and particularly preferably 100 nm or less.
  • the lower limit of the primary particle size of the copper oxide nanoparticles is not particularly limited, but is practically 4 nm or more.
  • the "primary particle size” refers to the diameter of the primary particle, and the circle equivalent diameter may be derived from the half-width of the peak in powder X-ray structure analysis.
  • the primary particle size of the copper oxide nanoparticles can also be measured using, for example, a particle size distribution measuring device using dynamic light scattering (DLS).
  • DLS dynamic light scattering
  • the black electrochromic material of the present invention may contain other electrochromic materials in addition to the copper oxide nanoparticles, which are the heat-treated product of basic copper carbonate.
  • the black electrochromic material of the present invention may contain the above-mentioned copper oxide nanoparticles in an amount of 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • one embodiment of the black electrochromic material of the present invention contains one or more of titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, and metallic iridium nanoparticles.
  • nanoparticles contain many with an average primary particle size of 10 to 50 nm, and nanoparticles of 5 to 30 nm in particular contribute effectively to the expression of performance. However, if the particles are coarse and have an average particle size of 100 ⁇ m or more, they cannot be made into paint due to considerations such as dispersibility and stability over time, and electrochromic properties are not expressed.
  • the paint of the present invention is a paint containing the above-mentioned black electrochromic material.
  • copper oxide nanoparticles which are a heat-treated product of basic copper carbonate, are dispersed in a weakly acidic solvent.
  • the method for producing a coating material of the present invention comprises the following steps: A first step of heating basic copper carbonate to obtain copper oxide nanoparticles; and A second step includes dispersing copper oxide nanoparticles in a weakly acidic solvent.
  • the solvent used is any material capable of dispersing copper oxide nanoparticles and not affecting the copper oxide nanoparticles.
  • water or alcohol is used as the solvent.
  • the alcohol one or more types are selected from isopropanol, ethanol, methanol, n-propanol, isobutanol, n-butanol, etc. From the viewpoint of improving the dispersibility of the copper oxide nanoparticles, for example, water is preferable.
  • the obtained copper oxide nanoparticles can be made into a paint by suitably dispersing them in an aqueous solution adjusted to a weak acidity using citric acid or the like.
  • the copper oxide nanoparticles used in the present invention are difficult to disperse in alkaline or neutral solvents, but can be easily dispersed in a weak acidic solvent containing citric acid or the like.
  • strong acids are not preferred because copper oxide dissolves in them.
  • citric acid can be dissolved in water as a solvent to adjust the pH, and then copper oxide nanoparticles can be added. If the pH of the solvent to which citric acid or the like is added is 3.0 or less, the copper oxide nanoparticles can be suitably dispersed.
  • the lower limit of the pH of the solvent is not particularly limited, but can be, for example, 2.0 or more.
  • the content (solid content) of copper oxide nanoparticles in the paint is not particularly limited and can be adjusted appropriately depending on the application, but can be, for example, in the range of 1% by mass to 20% by mass.
  • the paint of the present invention can exhibit a black color even when the content (solid content) of copper oxide nanoparticles in the paint is 1% by mass, and a black paint with excellent dispersibility can be obtained even when the content (solid content) is 20% by mass.
  • the paint of the present invention preferably has a zeta potential of -36 to -28 mV.
  • the paint of the present invention has a zeta potential in this range, it has excellent dispersibility, making it possible to prepare suitable thin films, color-changing electrodes, and electrochromic elements.
  • the coating material of the present invention may also contain a binder.
  • the binder is not particularly limited, and may be one or more binders selected from organic binders or inorganic binders.
  • organic binders include cellulose derivatives, vinyl resins, fluorine-based resins, silicone resins, acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins, and alkyd resins.
  • inorganic binders include products obtained by decomposing hydrolyzable silicon compounds such as alkyl silicates, silicon halides, and partial hydrolyzates thereof, organic polysiloxane compounds and polycondensates thereof, silica, colloidal silica, water glass, silicon compounds, phosphates such as zinc phosphate, metal oxides such as zinc oxide and zirconium oxide, heavy phosphates, cement, gypsum, lime, and enamel frits.
  • hydrolyzable silicon compounds such as alkyl silicates, silicon halides, and partial hydrolyzates thereof, organic polysiloxane compounds and polycondensates thereof, silica, colloidal silica, water glass, silicon compounds, phosphates such as zinc phosphate, metal oxides such as zinc oxide and zirconium oxide, heavy phosphates, cement, gypsum, lime, and enamel frits.
  • the binder one or more selected from, for example, polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), and hydroxyethyl cellulose (HEC).
  • PVA polyvinyl alcohol
  • CMC sodium carboxymethyl cellulose
  • HPC hydroxypropyl cellulose
  • HEC hydroxyethyl cellulose
  • the lower limit of the binder content is 0.1% by mass or more, preferably 0.15% by mass or more, based on the paint mass (i.e., when the total paint mass is 100% by mass).
  • the upper limit of the binder content is 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less, based on the paint mass.
  • additives may be blended into the paint.
  • additives include defoamers, crosslinking agents, curing catalysts, pigment dispersants, emulsifiers, film-forming agents, thickeners, neutralizing agents, preservatives, etc.
  • the paint of the present invention comprises a black electrochromic material containing one or more of titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, and metallic iridium nanoparticles dispersed in a weakly acidic solvent.
  • the mixed paint of the present invention includes the paint of the present invention containing the above-mentioned copper oxide nanoparticles and a paint containing another oxide-based electrochromic material.
  • the method for producing the mixed paint of the present invention also includes a step of mixing the paint of the present invention containing the above-mentioned copper oxide nanoparticles with a paint containing another oxide-based electrochromic material.
  • the other oxide-based electrochromic material to be mixed with the paint of the present invention containing copper oxide nanoparticles is not particularly limited as long as the black color effect of the copper oxide nanoparticles can be obtained, and may be, for example, one or more of metal oxide nanoparticles such as WO 3 , TiO 2 , NiO, Ir(OH) 2 , V 2 O 5 , Nb 2 O 5 , MoO 3 , TiN, and ZrO 2.
  • metal oxide nanoparticles such as WO 3 , TiO 2 , NiO, Ir(OH) 2 , V 2 O 5 , Nb 2 O 5 , MoO 3 , TiN, and ZrO 2.
  • the mixed paint of the present invention may be in a form in which the paint of the present invention containing the above-mentioned copper oxide nanoparticles is mixed with a paint containing at least one of titanium oxide nanoparticles, titanium nitride nanoparticles, nickel oxide nanoparticles, nickel hydroxide nanoparticles, zirconium oxide nanoparticles, and metal iridium nanoparticles.
  • copper oxide nanoparticles can be used as an additive and added to other oxide-based electrochromic materials to produce a paint.
  • the content (solid amount) of the copper oxide nanoparticles may be, for example, 0.1 to 5.0 mass% relative to the solid amount of the other oxide-based electrochromic materials.
  • the method of mixing the paint of the present invention with a paint containing another oxide-based electrochromic material is not particularly limited as long as it is possible to achieve complete mixing.
  • a paint containing another oxide-based electrochromic material for example, by mixing the paint of the present invention containing copper oxide nanoparticles with a nanoparticle dispersion of another oxide-based electrochromic material, and then applying and forming a film, a thin film in which two types of electrochromic materials are mixed at the nanoparticle level can be obtained.
  • the electrode layer is formed from a multilayer film having a thin film of the paint or mixed paint of the present invention containing a black electrochromic material.
  • the color-changeable electrode 100a in the form illustrated in FIG. 5 is constructed by laminating a first electrochromic layer 10, a first transparent electrode layer 40, and a first insulating layer 60.
  • the first electrochromic layer 10 is connected to one surface of the transparent electrode layer 40, and the other surface of the transparent electrode layer 40 (the surface opposite the first electrochromic layer 10) is connected to the first insulating layer 60.
  • the first electrochromic layer 10 is a thin film formed by a paint or mixed paint containing the black electrochromic material of the present invention described above.
  • the copper oxide nanoparticles contained in the paint are black in an oxidized state and colorless and transparent in a reduced state. That is, one embodiment of the method for producing a color-changeable electrode of the present invention includes a step of forming a thin film containing a black electrochromic material on an electrode layer using the paint or mixed paint of the present invention described above.
  • the thickness of the first electrochromic layer 10 is set appropriately depending on the purpose, and is, for example, 20 to 1500 nm.
  • the thickness of the first electrochromic layer 10 may or may not be constant (i.e., it may vary depending on the position in the surface direction).
  • the first transparent electrode layer (electrode layer) 40 is a layer made of a transparent conductive material.
  • a transparent conductive material there are no particular limitations on the conductive material as long as it is used as an electrochemical element and does not cause deterioration such as corrosion to a practical extent, and examples of the conductive material that can be used include conductive oxides such as indium tin oxide (ITO), zinc oxide, and those doped with metals such as aluminum, silver, and titanium, precious metals such as gold and platinum, alloys and metals having corrosion resistance due to a passivation film such as stainless steel and aluminum, and carbon materials such as graphene and carbon nanotubes.
  • ITO indium tin oxide
  • zinc oxide zinc oxide
  • metals such as aluminum, silver, and titanium
  • precious metals such as gold and platinum
  • alloys and metals having corrosion resistance due to a passivation film such as stainless steel and aluminum
  • carbon materials such as graphene and carbon nanotubes.
  • the thickness of the first transparent electrode layer 40 is set appropriately depending on the purpose, and is, for example, 100 to 300 nm.
  • the thickness of the first transparent electrode layer 40 may or may not be constant (i.e., it may vary depending on the position in the surface direction).
  • the thickness of the first transparent electrode layer 40 may be designed to be non-uniform. Specifically, the surface of the first transparent electrode layer 40 may be made uneven (i.e., the smoothness of the surface may be reduced).
  • the convex portions on the surface of the first transparent electrode layer 40 may be formed, for example, from a conductive material.
  • the first transparent electrode layer 40 may contain known additives for the purposes of improving adhesion with the first electrochromic layer 10 and suppressing corrosion.
  • known additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, tackifiers, color inhibitors, flame retardants, and antistatic agents.
  • the color-changeable electrode 100a when the color-changeable electrode 100a is intended for use in light-control glass, light-control films, etc., it must be transparent. Therefore, the embodiment shown in FIG. 5 illustrates the first transparent electrode layer 40, but the color-changeable electrode 100a of the present invention also includes a form in which a non-transparent electrode layer is used.
  • the first insulating layer 60 is a layer made of a transparent insulating material.
  • the first insulating layer 60 can be made of resin or glass.
  • resin include polyethylene terephthalate (PET), polycarbonate, and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the first insulating layer 60 may contain known additives such as an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a tackifier, a coloring inhibitor, a flame retardant, and an antistatic agent.
  • the thickness of the first insulating layer 60 and the second insulating layer 70 is, for example, 50 ⁇ m to 1.1 mm.
  • the thickness of the first insulating layer 60 and the second insulating layer 70 may or may not be constant (i.e., it may vary depending on the position in the surface direction).
  • the first insulating layer 60 is not necessarily required for the color-changeable electrode 100a of the present invention, and can be omitted.
  • FIG. 6 is a structural schematic diagram (cross-sectional view) showing an embodiment of an ECD of the present invention.
  • the ECD 200 has an electrolyte layer 30 sandwiched between a first color-changing electrode 100a and a second color-changing electrode 100b.
  • the ECD 200 is driven by applying a voltage to the first color-changeable electrode 100a and the second color-changeable electrode 100b. That is, the ECD 200 is driven in the following state 1 and state 2: (State 1) A state in which the first electrochromic layer 10 is in an oxidized state and the second electrochromic layer 20 is in a reduced state. (State 2) A color change between these states in which the first electrochromic layer 10 is in a reduced state and the second electrochromic layer 20 is in an oxidized state can be achieved by applying a voltage.
  • the ECD 200 when used as light control glass, the first transparent electrode layer 40 and the second transparent electrode layer 50 are used as the electrode layers, and a transparent material is used for the electrolyte. This is called a transmissive ECD.
  • a transmissive ECD When in the form of a transmissive ECD, the color of the ECD 200 is a mixed color of the first electrochromic layer 10 and the second electrochromic layer 20.
  • the color of the first electrochromic layer 10 becomes the color of the ECD 200 as is.
  • a reflective ECD the colors of the second electrochromic layer 20 and the electrode layer (conductive material) of the second color-variable electrode 100b are not limited.
  • the second electrochromic layer 20 In the case of a transmissive ECD, the second electrochromic layer 20 must have stable electrochemical properties and be made of a material that exhibits the required color change. On the other hand, in the case of a reflective ECD, the second electrochromic layer 20 only needs to have stable electrochemical properties.
  • the second color-variable electrode 100b may be made of an electrochromic material that is colorless (colorless and transparent) in an oxidized state and colored in a reduced state.
  • ECD200 includes a first electrochromic layer 10 (an example of a "thin film made of paint containing copper oxide nanoparticles"), a second electrochromic layer 20 (an example of a "metal cyano complex thin film”), an electrolyte layer 30, a first transparent electrode layer 40, a second transparent electrode layer 50, a first insulating layer 60, and a second insulating layer 70.
  • ECD200 is composed of a stack of these layers (10, 20, 30, 40, 50, 60, 70).
  • the electrolyte layer 30 is located between the first electrochromic layer 10 and the second electrochromic layer 20.
  • the first transparent electrode layer 40 is located on the surface of the first electrochromic layer 10 opposite the electrolyte layer 30.
  • the second transparent electrode layer 50 is located on the surface of the second electrochromic layer 20 opposite the electrolyte layer 30.
  • the first insulating layer 60 is located on the surface of the first transparent electrode layer 40 opposite the first electrochromic layer 10.
  • the second insulating layer 70 is located on the surface of the second transparent electrode layer 50 opposite the second electrochromic layer 20.
  • the first electrochromic layer 10 and the second electrochromic layer 20 are layers that have electrochromic properties, and their color changes reversibly due to an oxidation-reduction reaction (they reversibly change between a colored state and a decolored state).
  • the first electrochromic layer 10 turns black in the oxidized state, and decolorizes in the reduced state (becoming colorless and transparent).
  • the first color-changeable electrode 100a is configured by laminating the above-mentioned first electrochromic layer 10, the first transparent electrode layer 40, and the first insulating layer 60.
  • the first color-changeable electrode 100a is common to the above-mentioned color-changeable electrode of the present invention, and therefore, description thereof will be omitted below.
  • the second color-changeable electrode 100b is made of an electrochromic material and an electrode layer (conductive material), and may have the same structural freedom as the first color-changeable electrode 100a.
  • the second color-changeable electrode 100b may also be a mixture of multiple electrochromic materials.
  • the second color-changeable electrode 100b may be made of a material that reversibly causes an electrochemical oxidation-reduction reaction, and does not necessarily have to have different colors in the oxidized and reduced states.
  • the second color-variable electrode 100b is constructed by laminating a second electrochromic layer 20, a second transparent electrode layer 50, and a second insulating layer 70.
  • the second electrochromic layer 20 includes a material that changes color and decolor due to an oxidation-reduction reaction differently from the copper oxide nanoparticles used in the first electrochromic layer 10, and preferably includes metal cyano complex nanoparticles or other oxide nanoparticles. That is, the second electrochromic layer 20 includes a form such as a metal cyano complex thin film or another oxide thin film.
  • metal cyano complex nanoparticles or oxide nanoparticles are used in the second electrochromic layer 20
  • any type of nanoparticle can be used as long as it causes a reversible oxidation-reduction reaction.
  • Metal cyano complex or oxide nanoparticles are materials that become colored in an oxidized state and lose their color in a reduced state.
  • metal cyano complex nanoparticles are used in the second electrochromic layer 20.
  • the metal cyano complex particles particles of a Prussian blue type metal cyano complex represented by the general formula " AxM ⁇ [ M ⁇ (CN) 6 ] y.zH2O " are preferably used.
  • A is an atom selected from the group consisting of hydrogen, lithium, sodium, and potassium.
  • M ⁇ is one or more metal atoms selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium.
  • M ⁇ is one or more metal atoms selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper, in which x is 0 to 3, y is 0.3 to 1.5, and z is 0 to 30.
  • metal cyano complex one type represented by the above general formula may be used, or multiple types may be mixed and used.
  • the upper limit of the primary particle size in the metal cyano complex nanoparticles is, for example, 300 nm or less, preferably 100 nm or less, and more preferably 50 nm or less, from the viewpoint of increasing the specific surface area and improving the electrochemical response speed, and from the viewpoint of forming a smooth thin film.
  • the lower limit of the primary particle size in the metal cyano complex nanoparticles is not particularly limited, but is, for example, 4 nm or more, preferably 5 nm or more, and more preferably 6 nm or more.
  • the thickness of the second electrochromic layer 20 is set appropriately depending on the purpose, and is, for example, 500 to 3000 nm.
  • the thickness of the second electrochromic layer 20 may or may not be constant (i.e., it may vary depending on the position in the surface direction).
  • Electrolyte layer 30 The electrolyte layer 30 is a layer containing an electrolyte.
  • the first electrochromic layer 10 and the second electrochromic layer 20 cause an electrochromic reaction in the electrolyte.
  • the electrolyte used in the electrolyte layer 30 preferably contains a (trifluoromethanesulfonyl)imide salt.
  • the (trifluoromethanesulfonyl)imide salt includes one or more of bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, and sodium bis(trifluoromethanesulfonyl)imide. Among these, potassium bis(trifluoromethanesulfonyl)imide is preferred.
  • copper oxide nanoparticles can be dispersed in the electrolyte layer 30.
  • the electrolyte content in the electrolyte layer 30 is not particularly limited, but from the viewpoint of improving the electrochemical response speed in the ECD 200, it is, for example, 0.1 to 1.5 mol/kg, and preferably 0.5 to 1.5 mol/kg.
  • the electrolyte layer 30 may contain a solvent or resin in addition to the electrolyte.
  • a solvent capable of dissolving the electrolyte contained in the electrolyte layer 30 can be used, and examples of such solvents include chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate, aliphatic carboxylates such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, and methyl trimethylacetate, aromatic carboxylates such as methyl benzoate and ethyl benzoate, lactones such as ⁇ -butyrolactone and ⁇ -valerolactone, lactams such as ⁇ -caprolactam and N-methylpyrrolidone,
  • the resin contained in the electrolyte layer 30 is not particularly limited, and one or more types of resin may be selected from known resins such as acrylic resin, urethane resin, silicone resin, epoxy resin, vinyl chloride resin, ethylene resin, melamine resin, phenol resin, methyl methacrylate resin, polyvinyl alcohol resin, polyvinyl acetal resin, and polyethylene oxide resin.
  • resins such as acrylic resin, urethane resin, silicone resin, epoxy resin, vinyl chloride resin, ethylene resin, melamine resin, phenol resin, methyl methacrylate resin, polyvinyl alcohol resin, polyvinyl acetal resin, and polyethylene oxide resin.
  • the electrolyte layer 30 may contain various other additives as long as they do not impair the function of the electrolyte layer 30.
  • additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, tackifiers, color inhibitors, flame retardants, and antistatic agents.
  • the thickness of the electrolyte layer 30 is set appropriately depending on the purpose, and is, for example, 50 ⁇ m to 0.3 mm.
  • the thickness of the electrolyte layer 30 may or may not be constant (i.e., it may vary depending on the position in the surface direction).
  • ECD 200 changes between state 1 and state 2 when a voltage is applied.
  • ECD 200 exhibits a color change between black and transparent.
  • the manufacturing method of the electrochromic device (ECD) of the present invention includes a step of laminating a color-changeable electrode and an electrolyte layer.
  • An example of the manufacturing method of an ECD is described below.
  • a commercially available substrate with transparent electrodes e.g., ITO-coated glass
  • glass corresponds to the first insulating layer 60 and the second insulating layer 70.
  • Each of the two base materials is called the first substrate (second transparent electrode layer 50 + second insulating layer 70) and the second substrate (first transparent electrode layer 40 + first insulating layer 60).
  • a first film-forming substrate (second color-variable electrode 100b) is manufactured by forming a second electrochromic layer 20 on a first substrate using a coating method such as a wet coating process, such as slit coating, spin coating, bar coating, or spray coating.
  • a second film-forming substrate (first color-variable electrode 100a) is manufactured by forming a first electrochromic layer 10 on a second substrate using the same method.
  • An electrolyte layer 30 is formed on the first film-forming substrate (second color-variable electrode 100b) using a dispenser.
  • a sealing structure is formed around the periphery using UV-curable resin. Alternatively, this sealing structure can be formed using commercially available electronic device sealing tape, etc.
  • first color-variable electrode 100a first color-variable electrode 100a
  • second film-forming substrate 100b second color-variable electrode 100b
  • sealing tape there is no problem with bonding at room temperature and atmospheric pressure.
  • an ECD 200 consisting of a structure of first insulating layer 60/first transparent electrode layer 40/first electrochromic layer 10/electrolyte layer 30/second electrochromic layer 20/second transparent electrode layer 50/second insulating layer 70 is obtained.
  • the black electrochromic material, paint, and mixed paint of the present invention make it possible to realize a device (color-changeable electrode, electrochromic element) that can stably change color between black and transparent without using an organic electrochromic material.
  • This electrochromic element is useful, for example, for light-control glass, displays, indicators, and light-control mirrors.
  • the manufacturing method of the black electrochromic material, paint, and mixed paint of the present invention makes it easy to obtain black electrochromic materials, paints, and mixed paints that can stably achieve a color change from black to transparent.
  • the black electrochromic material and its manufacturing method, the paint and its manufacturing method, the mixed paint and its manufacturing method, the color-changeable electrode, and the electrochromic element of the present invention are not limited to the above embodiments.
  • Preparation Example 1 Preparation of Copper Oxide Nanoparticle Dispersed Paint A copper oxide nanoparticle dispersion was prepared as follows. In the first step, basic copper carbonate was heated in an electric furnace at 350° C. for 3 hours to obtain copper oxide nanoparticles. The X-ray diffraction result of the obtained copper oxide nanoparticles is shown in FIG.
  • a solvent with an adjusted pH was prepared by dissolving an arbitrary amount of citric acid in 50 g of water. For example, adding approximately 0.0020 g of citric acid to 20 g of water results in a pH of 3. 5 g of the copper oxide nanoparticles produced in the first step were suspended in the prepared solvent and stirred at 800 rpm for two days.
  • FIG 8. A photograph of the appearance of the paint with the obtained copper oxide nanoparticles dispersed is shown in Figure 8. As shown in Figure 8, it was confirmed that the copper oxide nanoparticles are suitably dispersed in the solvent at a pH of 3 or less, and a copper oxide nanoparticle-dispersed paint (hereinafter sometimes simply referred to as "paint”) can be obtained.
  • paint a copper oxide nanoparticle-dispersed paint
  • the particle size distribution of each paint produced relative to the solid copper oxide content is shown in Figure 9.
  • the paint obtained in Preparation Example 1 has a solid copper oxide nanoparticle content of 15% or less and an average particle size of 100 nm or less.
  • Preparation Example 2 Preparation of copper oxide nanoparticle thin film electrode Using the coating material obtained in Preparation Example 1, a thin film electrode was prepared as follows. In order to improve adhesion to the ITO-coated glass, PVA (polyvinyl alcohol) was added to the paint (copper oxide nanoparticle dispersion paint) prepared in Preparation Example 1. Using this paint, a copper oxide nanoparticle thin film was formed on the ITO-coated glass by spin coating to produce a copper oxide nanoparticle thin film electrode.
  • PVA polyvinyl alcohol
  • Example 1 Electrochemical properties of copper oxide nanoparticle thin film electrode
  • the copper oxide nanoparticle thin film electrode prepared in Preparation Example 2 was immersed in an electrolyte, and the visible light transmittance was evaluated using a spectrometer USB4000 manufactured by Ocean Photonics.
  • the electrolyte used was a LiClO 4 /PC (1 mol/kg) solution.
  • a cyclic voltammogram was obtained at a scan rate of 5 mV/sec, the material showed a CV curve as shown in FIG. 10. This demonstrated that the copper oxide nanoparticle thin film electrode prepared in Preparation Example 2 had electrochemical properties.
  • Example 2 Effect of the Amount of PVA Added When Forming a Copper Oxide Nanoparticle Thin Film Electrode
  • the effect of the amount of PVA added to the copper oxide nanoparticle dispersion paint was investigated.
  • Figure 11 shows the results of X-ray structural analysis of the copper oxide nanoparticle thin film electrode. As shown in Figure 11, it was confirmed that the thin film produced was copper oxide, regardless of the amount of PVA added.
  • Figure 12 shows the results of investigating the average particle size using a particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd.) using dynamic light scattering (DLS). As shown in Figure 12, even when 10 wt. % PVA was added to the solid amount of copper oxide nanoparticles, the average particle size was approximately 80 nm.
  • Figure 13 shows the results of measuring the zeta potential using a zeta potential measurement system (manufactured by Otsuka Electronics Co., Ltd.). As shown in Figure 13, the zeta potential was approximately -35 mV, regardless of the amount of PVA added.
  • Figure 14 shows the results of observing the surface structure of a copper oxide nanoparticle thin film electrode using an FE-SEM. As shown in Figure 14, the size of the copper oxide nanoparticles contained in the thin film was approximately 30 nm. Here too, no significant differences were observed depending on the amount of PVA added.
  • Figure 15 shows the results of acquiring a transmission spectrum when the electrochemical end potential was set to -1.6 V and +1.2 V. As shown in Figure 15, it was confirmed that the transmittance of the copper oxide nanoparticle thin film electrode changes with the electrochemical reaction.
  • Example 3 Dependence of electrochromic properties of copper oxide nanoparticle thin film electrode on film thickness
  • the electrochromic properties of the copper oxide nanoparticle thin film electrode also depend on the film thickness.
  • the film thickness was controlled by adjusting the rotation speed and time as shown in Table 1 below.
  • FIG. 16 is a diagram showing the change in optical transmission spectrum under each film formation condition.
  • the copper oxide nanoparticle thin film electrode formed at a rotation speed of 300 rpm has a large change in transmittance due to the redox reaction.
  • the transmission spectrum has almost no wavelength dependency between 450 nanometers and 650 nanometers, and a color change from transparent to gray (black) occurs.
  • T VIS visible light transmittance
  • Example 4 Preparation of mixed paint using copper oxide nanoparticle dispersion paint
  • the copper oxide nanoparticle dispersion paint prepared in Preparation Example 1 was added as an additive to 10 g of tungsten oxide nanoparticle dispersion paint with a solid content of 15 wt. %.
  • the copper oxide nanoparticle dispersion paint used here had a solid content of 2 wt. % and was added to the tungsten oxide nanoparticles at a solid content of 1% to obtain a mixed paint.
  • Figure 18 shows the change in the optical transmission spectrum of the thin-film electrode made from the mixed paint.
  • a KTFSI/PC (1 mol/kg) solution was used as the electrolyte.
  • the thin-film electrode made from the mixed paint has increased absorbance, especially on the long wavelength side (600 nm and above), compared to the thin-film electrode made only from tungsten oxide nanoparticle dispersion paint. From this, it was confirmed that by using copper oxide nanoparticle dispersion paint as an additive and mixing it with other oxide-based nanoparticle dispersion paint, the thin-film electrode characteristics are improved and the color change on the colored side shows a darker color tone.
  • Example 5 Electrochemical properties of thin-film electrodes using various nanoparticle paints It was found that various oxide materials can be used as black electrochromic materials by controlling their particle size and functionality.
  • paints with the particle size distribution shown in Figure 19 were prepared for TiO2 , TiN, Ir metal, and Ni(OH) 2 .
  • polyethylene glycol and propylene glycol were mixed as binders in a solid amount ratio of 1:1, and 10 wt.
  • the coating material was adjusted by adding 100% TiO2 and 100% TiN.
  • Films were formed on fluorine-doped SnO2 conductive glass (FTO glass) using spin coating conditions of a drop amount of 300 ⁇ L, a first rotation speed of 300 rpm, and a second rotation speed of 3000 rpm.
  • FTO glass fluorine-doped SnO2 conductive glass
  • the films were heated on a hot plate at 100°C for 30 minutes, and the dry film thicknesses obtained were TiO2 (220 nm), TiN (40 nm), Ir metal (220 nm), and NiO(OH) 2 (120 nm).
  • the appearance change accompanying the electrochemical redox reaction when each of the prepared thin film electrodes was immersed in an electrolyte is shown in Figure 20.
  • the electrolyte used was a LiTFSI/PC (1 mol/kg) solution.
  • the WO3 thin film electrode of the comparative example is dark blue, but the thin film electrodes of all other materials are black.
  • FIG. 21 shows the change in the optical transmission spectrum in the ultraviolet, visible, and near infrared region at 250-2500 nm for each thin-film electrode prepared.
  • the electrolyte is the same as above.
  • the WO 3 thin-film electrode in the colored state, has a transmittance of only a few tens of percent, but in the visible light region, all other materials have a transmittance of 10% or less, and are black.
  • FIG. 22 shows the chromaticity calculated from the obtained data.
  • an index of brightness which is also the degree of blackening, TiO 2 , TiN, and CuO are about 95% in the decolorized state and a few percent (sometimes less than 1%) in the colored state, and it is clear that they are blackened as numerical data.
  • Figure 23 shows the time change in the optical transmission spectrum of each of the thin-film electrodes fabricated in the ultraviolet, visible, and near-infrared region at 250 to 2500 nm.
  • the electrolyte is the same as above.
  • application of a voltage of -2.5 V results in a transition to a colored state, and a gradual attenuation of transmittance.
  • This response speed is determined by the applied voltage, sample size, and type and concentration of electrolyte, but because it has memory properties, this transition state can be maintained even when the applied voltage is stopped. It was therefore confirmed that each thin-film electrode has the functionality to allow arbitrary dimming in multiple stages.
  • Example 6 Electrochemical Properties of Thin-Film Electrodes Using Zirconium Oxide Nanoparticle Paint As in Example 5, a paint having the particle size distribution shown in Fig. 24 was prepared for ZrO2 .
  • the prepared paint was applied to fluorine-doped SnO2 conductive glass (FTO glass) by spin coating under the following conditions: drop amount 300 ⁇ L, first rotation speed 300 rpm, second rotation speed 3000 rpm, and after the film formation, heating was performed on a hot plate at 100°C for 30 minutes, resulting in a dry film thickness of ZrO2 (80 nm).
  • FTO glass fluorine-doped SnO2 conductive glass
  • the appearance change accompanying the electrochemical redox reaction when the fabricated ZrO2 thin film electrode was immersed in an electrolyte is shown in Figure 25.
  • the electrolyte used was a LiTFSI/PC (1 mol/kg) solution.
  • the ZrO2 thin film electrode exhibited a black color.
  • First electrochromic layer 20 Second electrochromic layer 30: Electrolyte layer 40: First transparent electrode layer 50: Second transparent electrode layer 60: First insulating layer 70: Second insulating layer 100a: First color-variable electrode 100b: Second color-variable electrode 200: ECD

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PCT/JP2023/043811 2022-12-07 2023-12-07 黒色エレクトロクロミック材料およびその製造方法、塗料およびその製造方法、混合塗料およびその製造方法、色可変電極およびその製造方法およびエレクトロクロミック素子 Ceased WO2024122611A1 (ja)

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