JP5123749B2 - Method for reversibly changing reflectance, element thereof, method for manufacturing the element, transmittance variable element, and reflectance variable mirror - Google Patents

Description

  The present invention relates to a method for reversibly changing the reflectance, an element for reversibly changing the reflectance, a method for manufacturing the element, a transmittance variable element, and a reflectance variable mirror.

  Conventional elements that change optical characteristics such as transmittance and reflectance include electrochromic elements, thermochromic elements, photochromic elements, and liquid crystal elements. Patent Document 1 listed below describes a variable reflectance mirror for automobiles using an electrochromic element. Patent Document 2 below describes an all-solid-state reflective dimming electrochromic element. Patent Document 3 below describes a reflective light-control thin film material using a magnesium-niobium alloy thin film. Patent Document 4 listed below describes a light control mirror glass using a magnesium / nickel alloy thin film.

Japanese Patent Laid-Open No. 10-138832 JP 2008-40422 A JP 2008-20590 A JP 2004-139134 A

  The present invention seeks to provide a method for reversibly changing the reflectivity by a mechanism different from the conventional method, an element for reversibly changing the reflectivity, a method for manufacturing the element, a variable transmittance element, and a variable reflectivity mirror. Is.

In the method of reversibly changing the reflectance according to the present invention, an electrode pair is arranged with a gap therebetween, and the gap is reversibly ionized by a metal ion and an electrode reaction in a non-aqueous solvent containing methanol. Filled with an electrolyte solution in which a compound material is dispersed, and ionizes the compound material to the same polarity as the metal ions according to a change in the electric field between the electrode pairs, and the metal ions and the ionized compounds in the electrolyte solution The material is deposited on the surface of one electrode by electrophoresis to form a mirror, and conversely, the metal ion and the ionized compound are separated from the surface of the electrode and the compound material is neutralized. By changing, the reflectance of the surface of the electrode is reversibly changed.

The element of this invention whose reversibility changes reversibly is reversible by at least metal ions and an electrode reaction in a non-aqueous solvent containing methanol and filled in the gap with an electrode pair arranged with a gap. In accordance with a change in the electric field between the electrode pair, and the compound material is ionized to the same polarity as the metal ions and in the electrolyte solution. The state in which the metal ions and the ionized compound material are deposited on the surface of one electrode by electrophoresis to become a mirror, and conversely, the metal ions and the ionized compound are detached from the surface of the electrode and the compound material is removed. By changing to a neutralized state, the reflectance of the surface of the electrode changes reversibly. In this element, the metal ions may be one or more metal ions selected from, for example, silver, aluminum, cobalt, copper, nickel, molybdenum, iridium, platinum, and ruthenium. The compound material that is reversibly ionized by the electrode reaction can be, for example, a complex (ferrocene or the like). The non-aqueous solvent may contain, for example, methanol containing at least one selected from tetraethylammonium tetrafluoroborate-propylene carbonate, γ-butyrolactone, and sulfolane as a main component.

  The element of the present invention whose reflectivity reversibly changes is, for example, a transparent conductive material in which at least one electrode constituting the electrode pair is composed of a single metal, or is coated on the surface of a glass substrate, a resin substrate or a resin film. It may be composed of a film or a metal film. In the element of the present invention in which the reflectance changes reversibly, for example, when a voltage is applied between the electrode pair, the metal ions and the ionized compound material are deposited on the surface of one electrode by electrophoresis. By short-circuiting or opening the electrode pair from the state, the metal ions and the ionized compound material can be released from the surface of the electrode, and the ionized compound material can be neutralized. In the element of the present invention in which the reflectance is reversibly changed, any one or more of a thickener, PMMA, polyol isocyanate, and a polymer may be added to the electrolytic solution to make the electrolytic solution into a gel. it can. In the element of the present invention in which the reflectance changes reversibly, an ultraviolet absorber can be added to the electrolytic solution.

The method of manufacturing a device having a reversible change in reflectance according to the present invention comprises dissolving NiCl ₂ in dehydrated methanol, and at least one selected from tetraethylammonium tetrafluoroborate-propylene carbonate, γ-butyrolactone, and sulfolane. A non-aqueous solvent and a compound material that is reversibly ionized by an electrode reaction are added to prepare an electrolyte solution in which a metal ion and a compound material that is reversibly ionized by an electrode reaction are dispersed in the non-aqueous solvent. In the gap between the electrode pairs, and the compound material is ionized to the same polarity as the metal ions according to the change in the electric field between the electrode pairs, and the metal ions and the ionized compounds in the electrolytic solution The material is deposited on the surface of one electrode by electrophoresis to become a mirror, and conversely, the metal ions and the ions The compound is released from the surface of the electrode and changed to a state in which the compound material is neutralized to produce a device in which the reflectance of the electrode surface reversibly changes.

The transmittance variable element according to the present invention includes two transparent substrates disposed to face each other with a gap, transparent conductive films respectively formed on opposite surfaces of the two transparent substrates, and filled in the gap. An electrolyte solution in which a metal ion and a compound material that is reversibly ionized by an electrode reaction are dispersed in a non-aqueous solvent containing methanol, and the compound material according to a change in the electric field between the transparent conductive film pair In a state where the ion is ionized to the same polarity as the metal ion and the metal ion and the ionized compound material in the electrolyte are deposited on the surface of any one of the transparent conductive films by electrophoresis to form a mirror. The metal ion and the ionized compound are separated from the surface of the transparent conductive film, and the compound material is changed to a neutral state, and the reflectance of the surface of the transparent conductive film is reversibly changed. Serial transmission as viewed through the two transparent substrates in which reversibly changes.

The reflectivity variable mirror according to the present invention is disposed opposite to a transparent substrate having a transparent conductive film formed on the back surface thereof, with a gap between the transparent substrate and the transparent substrate on the back surface side of the transparent substrate. A back member that is opaque when viewed from the side, and an electrolytic solution in which a metal material and a compound material that is reversibly ionized by an electrode reaction are dispersed in a methanol-containing nonaqueous solvent that is filled in the gap. The compound material is ionized to the same polarity as the metal ion in response to a change in the electric field between the transparent conductive film and the electrode of the back member, and the metal ion in the electrolyte and the ionized compound material are electrophoresed. leaving life-and-death and state in which the mirror is deposited on either surface of the electrode of the transparent conductive film and the back member, a compound the metal ions and the ionized reversed from the surface by The compound material was changed to a state to neutralize, the reflectivity of the surface is changed reversibly, with in reflectance viewed from the front side of the transparent substrate is one which reversibly changes.

<< Embodiment 1: Embodiment of Variable Transmission Element >>
An embodiment in which the element of the present invention is configured as a transmittance variable element will be described below. In FIG. 1, the transmittance variable element 10 includes two transparent substrates 14 and 16 made of glass or resin and arranged to face each other with a gap 12 therebetween. Transparent conductive films 18 and 20 constituting electrode pairs are formed on opposing surfaces of the transparent substrates 14 and 16, respectively. The transparent conductive films 18 and 20 are made of, for example, ITO (indium tin oxide), tin oxide, zinc oxide or the like. The gap 12 is filled with an electrolytic solution 22. The space around the gap 12 is sealed with a sealing material 24. The electrolyte 22 is composed of tetraethylammonium tetrafluoroborate-propylene carbonate (TEABF ₄ -PC) as a main component and a non-aqueous solvent 25 containing methanol, and as a solute, a metal cation 26 (for example, Ni ²⁺ ) and an anion 28 (for example, Cl ^- ), A compound material 30 (for example, ferrocene) that is reversibly ionized by an electrode reaction is dispersed. In order to prevent the electrolytic solution 22 from leaking out of the gap 12 when the transparent substrates 14 and 16 are damaged, a thickener, PMMA, polyol isocyanate, a polymer, or the like is added to the electrolytic solution 22 to perform electrolysis. The liquid 22 can also be gelled. Further, in order to prevent the solvent from being deteriorated by ultraviolet rays irradiated from the outside, an ultraviolet absorber can be added to the electrolytic solution 22. One end portions of lead wires 32 and 34 are connected to the transparent conductive films 18 and 20, respectively. A series connection circuit of a switch 36 and a DC power source 38 is connected between the other ends of the lead wires 32 and 34. A switch 40 is connected between the lead wires 32 and 34 in parallel with the series connection circuit of the switch 36 and the DC power supply 38. The switches 36 and 40 are turned on and off in opposite directions in conjunction with each other.

  The operation of the transmittance variable element 10 having the above configuration will be described. As shown in FIG. 1, when the switch 36 is turned off and the switch 40 is turned on, the transparent conductive films 18 and 20 are short-circuited, and no electric field is generated between the transparent conductive films 18 and 20. Accordingly, the metal cation 26, the anion 28, and the compound material 30 are dispersed in the electrolytic solution 22. At this time, the compound material 30 is in a neutral state (non-ionized state). At this time, the electrolytic solution 22 is transparent, and the transmittance variable element 10 is transparent in the entire thickness direction from the transparent substrate 14 to the transparent substrate 16.

  When the switch 36 is turned on and the switch 40 is turned off as shown in FIG. 2 from the state of FIG. 1, the voltage of the DC power supply 38 is applied between the transparent conductive films 18 and 20 (the transparent conductive film 18 is the positive electrode and the transparent conductive film 20 An electric field is generated between the transparent conductive films 18 and 20. This electric field causes the compound material 30 in the electrolytic solution 22 to undergo an oxidation reaction and become cationized. Then, the metal cation 26 and the cationized compound material 30 in the electrolytic solution 22 are moved and deposited on the surface of the electrode having the opposite polarity to the both ions 26 and 30, that is, the negative electrode 20 by electrophoresis, and the anion 28 is positive. Move to electrode 18. A reflective film is deposited on the surface of the negative electrode 20 by the metal cation 26 deposited on the surface of the negative electrode 20. Thereby, the transmittance of the variable transmittance element 10 increases, and the transmittance decreases to become a mirror or a half mirror. The voltage applied between the transparent conductive films 18 and 20 can be varied stepwise or steplessly so that the reflectance and transmittance can be adjusted stepwise or steplessly.

  When the switch 36 is turned off again from the state shown in FIG. 2 and the switch 40 is turned on again, the transparent conductive films 18 and 20 are short-circuited, and the electric field between the transparent conductive films 18 and 20 disappears. As a result, the metal cation 26 and the compound material 30 are separated from the surface of the negative electrode 20, and the compound material 30 undergoes a reduction reaction and returns to the original neutral state. The anions 28 are separated from the surface of the positive electrode 18 and dispersed in the electrolytic solution 22. As a result, the transmittance of the transmittance variable element 10 decreases, and the transmittance increases to return to the original transparent state. In addition, since the electric field between both electrodes 18 and 20 disappears by opening both electrodes 18 and 20 instead of short-circuiting both electrodes 18 and 20, the metal cation 26 is detached from the negative electrode 20. Thus, the transmittance variable element 10 can be returned to the original transparent state.

As described above, the reflectance and transmittance of the transmittance variable element 10 can be reversibly changed by applying an electric field between the electrodes 18 and 20 and canceling the application of the electric field. In the process of this reversible operation, an electrode reaction does not occur (or hardly occurs) between the metal cation 26 and the negative electrode 20, so that the metal cation 26 keeps its ionic state, and only the added compound material 30 is present. Since an electrode reaction occurs, little current flows as a whole. Further, as shown in FIG. 2, in the state where the movement of the metal cation 26, the compound material 30 and the anion 28 is completed, even if the voltage is continuously applied from the DC power source 38, almost no current flows, so that power consumption hardly occurs. The electrode reaction of ferrocene in the above operation is as follows.

  The transmittance variable element 10 can be suitably used for applications such as, for example, a building light control window glass and an automobile light control window glass. That is, by reducing the transmittance (increasing the reflectivity) in summer to reflect ultraviolet rays and infrared rays to increase indoor cooling efficiency, and in the winter, increasing the transmittance (decreasing reflectivity) to increase indoor heating efficiency Can be increased. As a result, an energy saving effect can be obtained. Further, by reducing the transmittance (increasing the reflectance), it is possible to obtain a blinding effect with respect to the line of sight from the outside.

  The transmittance variable element 10 can also be used as an alternative device for the diaphragm of the camera. That is, the transmittance variable element 10 is arranged on the optical axis in the camera, and the voltage applied between the electrodes 18 and 20 is varied stepwise or steplessly to vary the transmittance of the transmittance variable element 10 stepwise. By adjusting in a stepless manner or steplessly, it is possible to form a throttle portion that does not have a mechanical operation portion.

  The transmittance variable element 10 can also be configured as a display body by metal reflection by dividing the transparent conductive film 20 into segments and applying a voltage to each segment.

<Example>
An embodiment of the transmittance variable element 10 of FIG. 1 will be described. A procedure for manufacturing and using the variable transmittance element 10 will be described. Here, a method described in JP-A-2007-103464 is used as a method for dissolving metal ions in a non-aqueous solvent.
(1) 5 wt% anhydrous NiCl ₂ is dissolved in dehydrated methanol in an N ² atmosphere so that moisture does not enter.
(2) The solution obtained in (1) above and 0.8 mol / liter of tetraethylammonium tetrafluoroborate-propylene carbonate solution are mixed at a volume ratio of 1: 9.
(3) 0.01 to 0.03 mol / liter of ferrocene is added to the solution obtained in the above (2) to prepare the electrolytic solution 22. The prepared electrolytic solution 22 is composed of tetraethylammonium tetrafluoroborate-propylene carbonate as a main component and mixed with methanol in a non-aqueous solvent 25, Ni ²⁺ as a metal cation 26, Cl ⁻ as an anion 28, an electrode Ferrocene as the compound material 30 that is reversibly ionized by the reaction is in a dispersed state. At this time, ferrocene is in a neutral state (non-ionized state).
(4) Filling the gap 12 (gap length: 1 mm) between the transparent substrates 14 and 16 arranged opposite to each other by forming the transparent conductive films 18 and 20 on the opposite surfaces, respectively, with the electrolytic solution 22 adjusted in the above (3). To do. After filling, the periphery of the gap 12 is sealed with a sealing material 24 to complete the transmittance variable element 10. The completed transmittance variable element 10 is transparent in the entire thickness direction (since the electrolytic solution 22 contains ferrocene, it is slightly yellowish transparent).
(5) An electrical circuit is connected to the completed transmittance variable element 10 as shown in FIG. 1, and the switch 36 is turned on and the switch 40 is turned off as shown in FIG. A voltage of 2V was applied. As a result, Ni ^2+, which is the metal cation 26, was deposited on the negative electrode 20 and a reflective film was deposited, and it became a colorless mirror when viewed through the transparent substrate 16 from the front side of the transparent substrate 16.
(6) When the switch 36 is turned off as shown in FIG. 1 from the state (5) and the switch 40 is turned on and the electrodes 18 and 20 are short-circuited, the reflective film disappears and the original transparent state is restored. Even when both the switches 36 and 40 were turned off from the state (5) above and the electrodes 18 and 20 were opened, the reflective film disappeared and the original transparent state was restored.

<Comparative example>
As a comparative example, an experiment similar to the above example was performed by adjusting the electrolytic solution 22 to which ferrocene was not added. As a result, when a voltage of 2 V was applied to both the electrodes 18 and 20, a reflective film was deposited on the negative electrode 20 to form a mirror, but after that both the electrodes 18 and 20 were short-circuited or opened to remain in the mirror state. There was no return to the original transparent state. Therefore, according to the examples, it was found that the mobility of metal ions is increased by adding ferrocene (compound material that is ionized reversibly by electrode reaction). The reason why such a difference occurs is not yet clear, but as one speculation, when ferrocene is not added, an electrode reaction occurs between the metal ion and the negative electrode 20 when the metal ion moves to the surface of the negative electrode. When metal ions are plated on the negative electrode 20 (that is, the metal ions do not return to the original state dispersed in the electrolytic solution 22), when ferrocene is added, ionized ferrocene and metal ions are mixed. Since it moves to the surface of the negative electrode in a state, it is considered that an electrode reaction is unlikely to occur between the metal ions and the negative electrode 20 (it is difficult to be plated).

<< Embodiment 2: Embodiment of a reflectivity variable mirror >>
An embodiment in which the element of the present invention is configured as a variable reflectivity mirror will be described below. The same reference numerals are used for portions common to the first embodiment. In FIG. 3, the reflectivity variable mirror 42 includes an opaque substrate 44 and a transparent substrate 16 that are arranged to face each other with a gap 12 therebetween. The opaque substrate 44 is made of a substrate made of glass, ceramics, resin, metal or the like whose surface is dark (black, etc.), for example, and has a low reflectance. Transparent conductive films 18 and 20 constituting electrode pairs are formed on opposing surfaces of the opaque substrate 44 and the transparent substrate 16, respectively. The gap 12 is filled with an electrolytic solution 22. The space around the gap 12 is sealed with a sealing material 24. The electrolytic solution 22 is the same as that used in the first embodiment, and a non-aqueous solvent 25 containing tetraethylammonium tetrafluoroborate-propylene carbonate as a main component and containing methanol, a metal cation 26 (for example, Ni ²⁺ ) as a solute, An anion 28 (for example, Cl ⁻ ) and a compound material 30 (for example, ferrocene) that is reversibly ionized by an electrode reaction are dispersed. In order to prevent the electrolytic solution 22 from leaking out of the gap 12 when the opaque substrate 44 and the transparent substrate 16 are damaged, a thickener, PMMA, polyol isocyanate, polymer, or the like is added to the electrolytic solution 22. The electrolyte solution 22 can also be gelled. Further, in order to prevent the solvent from being deteriorated by ultraviolet rays irradiated from the outside, an ultraviolet absorber can be added to the electrolytic solution 22. One end portions of lead wires 32 and 34 are connected to the transparent conductive films 18 and 20, respectively. A series connection circuit of a switch 36 and a DC power source 38 is connected between the other ends of the lead wires 32 and 34. A switch 40 is connected between the lead wires 32 and 34 in parallel with the series connection circuit of the switch 36 and the DC power supply 38. The switches 36 and 40 are turned on and off in opposite directions in conjunction with each other.

  The operation of the reflectivity variable mirror 42 having the above configuration will be described. When the switch 36 is turned off and the switch 40 is turned on as shown in FIG. 3, the transparent conductive films 18 and 20 are short-circuited, and no electric field is generated between the transparent conductive films 18 and 20. Accordingly, the metal cation 26, the anion 28, and the compound material 30 are dispersed in the electrolytic solution 22. At this time, the compound material 30 is in a neutral state (non-ionized state). At this time, the electrolytic solution 22 is transparent, and light incident from the surface side of the transparent substrate 16 strikes the opaque substrate 44 and is almost absorbed. Therefore, the reflectance seen from the front side of the transparent substrate 16 is low at this time.

  When the switch 36 is turned on and the switch 40 is turned off as shown in FIG. 4 from the state of FIG. 3, the voltage of the DC power supply 38 is applied between the transparent conductive films 18 and 20 (the transparent conductive film 18 is the positive electrode, the transparent conductive film 20 An electric field is generated between the transparent conductive films 18 and 20. This electric field causes the compound material 30 to oxidize by causing an oxidation reaction. Then, the metal cation 26 and the cationized compound material 30 in the electrolytic solution 22 are moved and deposited on the surface of the electrode having the opposite polarity to the both ions 26 and 30, that is, the negative electrode 20 by electrophoresis, and the anion 28 is positive. Move to electrode 18. A reflective film is deposited on the surface of the negative electrode 20 by the metal cation 26 deposited on the surface of the negative electrode 20. As a result, the reflectance of the variable reflectivity mirror 42 as viewed from the front side of the transparent substrate 16 increases. The voltage applied between the transparent conductive films 18 and 20 can be varied stepwise or steplessly so that the reflectance can be adjusted stepwise or steplessly.

  When the switch 36 is turned off again as shown in FIG. 3 from the state of FIG. 4 and the switch 40 is turned on, the transparent conductive films 18 and 20 are short-circuited, and the electric field between the transparent conductive films 18 and 20 disappears. As a result, the metal cation 26 and the compound material 30 are separated from the surface of the negative electrode 20, and the compound material 30 undergoes a reduction reaction and returns to the original neutral state. The anions 28 are separated from the surface of the positive electrode 18 and dispersed in the electrolytic solution 22. As a result, the reflectivity variable mirror 42 returns to the original state as the reflectivity viewed from the front side of the transparent substrate 16 is lowered. In addition, since the electric field between both electrodes 18 and 20 disappears by opening both electrodes 18 and 20 instead of short-circuiting both electrodes 18 and 20, the metal cation 26 is detached from the negative electrode 20. Thus, the reflectivity of the reflectivity variable mirror 42 can be returned to the original low reflectivity state.

  As described above, by applying an electric field between the electrodes 18 and 20 and canceling the application of the electric field, the reflectance of the reflectivity variable mirror 42 viewed from the front surface side of the transparent substrate 16 is reversibly changed. Can be made. In the process of this reversible operation, an electrode reaction does not occur (or hardly occurs) between the metal cation 26 and the negative electrode 20, so that the metal cation 26 keeps its ionic state, and only the added compound material 30 is present. Since an electrode reaction occurs, little current flows as a whole. Further, as shown in FIG. 4, in the state where the movement of the metal cation 26, the compound material 30 and the anion 28 is completed, even if the voltage is continuously applied from the DC power source 38, almost no current flows, so that power consumption hardly occurs.

  The reflectivity variable mirror 42 can be used, for example, as a vehicle anti-glare mirror. The reflectivity variable mirror 42 can also be configured as a display body by metal reflection by dividing the transparent conductive film 20 into segments and applying a voltage to each segment.

  In each of the above-described embodiments, the case where nickel is used as the metal forming the metal ions has been described. However, silver, aluminum, cobalt, copper, molybdenum, iridium, platinum, ruthenium, and other metals can be used. In each of the embodiments described above, the case where ferrocene is used as a compound material that is reversibly ionized by an electrode reaction has been described. However, it has similar properties to ferrocene and is used as an oxidative coloring electrochromic material similar to ferrocene. It is considered that phenazine, other electrochromic materials, and other various compound materials that ionize reversibly by electrode reaction can be used. In each of the above embodiments, tetraethylammonium tetrafluoroborate-propylene carbonate is used as the non-aqueous solvent, but γ-butyrolactone, sulfolane, or the like can also be used. In each of the above embodiments, a glass substrate, a resin substrate, or the like is used as a base material for forming the transparent conductive films 18 and 20, but a conductive film can be formed on the surface using a resin film as a base material. .

  In the second embodiment, the conductive film 18 is formed of a transparent conductive film, but a metal film (opaque conductive film) can also be used. In the second embodiment, the transparent conductive film 18 formed on the surface of the opaque substrate 44 is used. However, instead of the combination of the opaque substrate 44 and the transparent conductive film 18, a single metal plate is disposed, and the metal plate A single substance can also be used as a substrate and electrode.

It is a schematic cross-sectional view and an electric circuit diagram showing an embodiment of a transmittance variable element according to the present invention, and shows a state when both electrodes are short-circuited. It is a figure which shows a state when a voltage is applied between both electrodes in the transmittance | permeability variable element of FIG. It is a schematic cross-sectional view and an electric circuit diagram showing an embodiment of a reflectivity variable mirror according to the present invention, and shows a state when both electrodes are short-circuited. It is a figure which shows a state when a voltage is applied between both electrodes in the reflectivity variable mirror of FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Variable transmittance element, 12 ... Air gap, 14, 16 ... Transparent substrate, 18, 20 ... Transparent conductive film (electrode pair), 22 ... Electrolytic solution, 24 ... Sealing material, 25 ... Nonaqueous solvent, 26 ... Metal positive Ion, 28 ... anion, 30 ... Compound material that ionizes reversibly by electrode reaction, 32, 34 ... Lead wire, 36, 40 ... Switch, 38 ... DC power supply, 42 ... Reflectance variable mirror, 44 ... Opaque substrate

Claims (11)

Place electrode pairs across the gap,
The void is filled with an electrolytic solution in which at least metal ions and a compound material that is reversibly ionized by an electrode reaction are dispersed in a non-aqueous solvent containing methanol ,
The compound material is ionized to the same polarity as the metal ion in accordance with a change in the electric field between the electrode pairs, and the metal ion in the electrolyte and the ionized compound material are deposited on the surface of one electrode by electrophoresis. And changing the state to be a mirror, and conversely, separating the metal ions and the ionized compound from the surface of the electrode and neutralizing the compound material, thereby changing the reflectivity of the surface of the electrode. Reversible change method.   The method of claim 1, wherein the compound material is ferrocene.   The method according to claim 1 or 2, wherein the non-aqueous solvent contains as a main component at least one selected from tetraethylammonium tetrafluoroborate-propylene carbonate, γ-butyrolactone, and sulfolane.   The method according to claim 1, wherein an ultraviolet absorber is added to the electrolytic solution. An electrode pair disposed with a gap therebetween, and an electrolyte solution in which at least metal ions and a compound material that is reversibly ionized by an electrode reaction are dispersed in a methanol-containing nonaqueous solvent filled in the gap. And
The compound material is ionized to the same polarity as the metal ions in accordance with the change in the electric field between the electrode pairs, and the metal ions and the ionized compound material in the electrolyte are deposited on the surface of one electrode by electrophoresis. The state of being a mirror, and conversely, the metal ions and the ionized compound are separated from the surface of the electrode and the compound material is neutralized, and the reflectance of the surface of the electrode is changed. An element that changes reversibly. The device according to claim 5 , wherein the compound material is ferrocene. The nonaqueous solvent is tetraethylammonium tetrafluoroborate - propylene carbonate, .gamma.-butyrolactone, element according to claim 5 or 6 shall be the main component at least one selected from sulfolane. The method according to any one of claims 5 to 7 formed by adding an ultraviolet absorber to the electrolyte. NiCl ₂ is dissolved in dehydrated methanol, and at least one non-aqueous solvent selected from tetraethylammonium tetrafluoroborate-propylene carbonate, γ-butyrolactone, and sulfolane and a compound material that is ionized reversibly by an electrode reaction are added thereto. Prepare an electrolyte solution in which a metal ion and a compound material that is reversibly ionized by an electrode reaction are dispersed in a non-aqueous solvent,
Filling the gap between the electrode pair with the electrolyte,
The compound material is ionized to the same polarity as the metal ions in accordance with the change in the electric field between the electrode pairs, and the metal ions and the ionized compound material in the electrolyte are deposited on the surface of one electrode by electrophoresis. The state of being a mirror, and conversely, the metal ions and the ionized compound are separated from the surface of the electrode and the compound material is neutralized, and the reflectance of the surface of the electrode is changed. A method for producing a reversibly changing element. Two transparent substrates disposed opposite each other with a gap between them;
Transparent conductive films respectively formed on opposing surfaces of the two transparent substrates;
An electrolyte solution in which a metal material and a compound material that is reversibly ionized by an electrode reaction are dispersed in a methanol-containing nonaqueous solvent filled in the voids,
The compound material is ionized to the same polarity as the metal ion according to a change in the electric field between the transparent conductive film pair, and the metal ion and the ionized compound material in the electrolyte solution are either of the above transparent by electrophoresis. A state of being deposited on the surface of the conductive film to become a mirror, and conversely, a state in which the metal ions and the ionized compound are separated from the surface of the transparent conductive film and the compound material is neutralized, A transmittance variable element in which the reflectance of the surface of the transparent conductive film reversibly changes, and thus the transmittance seen through both transparent substrates changes reversibly. A transparent substrate having a transparent conductive film formed on the back surface;
A back member disposed opposite to the transparent substrate with a gap on the back side of the transparent substrate, at least the front surface constituting an electrode, and opaque when viewed from the front side;
An electrolyte solution in which a metal material and a compound material that is reversibly ionized by an electrode reaction are dispersed in a methanol-containing nonaqueous solvent filled in the voids,
In response to a change in the electric field between the transparent conductive film and the electrode of the back member, the compound material is ionized to the same polarity as the metal ion, and the metal ion and the ionized compound material in the electrolyte are electrophoresed. A state of being deposited on one of the surfaces of the transparent conductive film and the electrode of the back member to become a mirror, and conversely, the metal ions and the ionized compound are separated from the surface and the compound material is neutralized. The reflectivity variable mirror in which the reflectivity of the surface changes reversibly and the reflectivity seen from the front side of the transparent substrate changes reversibly.

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