JP2012021212A - Electron supplier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron supplier which causes no electrolyte leakage, is excellent in handleability, can be produced easily using an inexpensive material, and can supply sufficient electrons even in the case where use of a transparent conductive film such as an ITO film is not preferred.SOLUTION: An electron supplier 10 includes, in the following order, a solidified sheet-shaped first electrolyte layer 13, a conductive layer 11 including a conductive substrate prepared by coating and/or impregnating a fiber substrate and/or a film substrate with a conductive material including carbon as a main component, a semiconductor layer 12 which generates electrons with electromagnetic waves and a solidified sheet-shaped second electrolyte layer 14 through which electromagnetic waves can be transmitted. The second electrolyte layer 14 is formed such that the charge can transfer between the second electrolyte layer 14 and the first electrolyte layer 13 by their mutual contact or access.

Description

  The present invention relates to an electron supplier that can be used for a dye-sensitized solar cell, an anticorrosion structure such as a reinforcing bar in concrete, an optical sensor, and the like.

For example, a dye-sensitized solar cell (DSC) is a solar cell having an electrochemical cell structure typified by an iodine solution. The DSC is formed between a working electrode made of a semiconductor layer such as a titania layer formed by adsorbing a dye on a transparent conductive substrate in which a transparent conductive film is laminated on a transparent glass plate or the like and a counter electrode made of a transparent or opaque conductive substrate. It has a simple structure in which an electrolyte solution (electrolytic solution) such as an iodine solution is disposed.
Therefore, DSC is considered to be a low-cost solar cell because it is inexpensive and does not require large-scale equipment for production.

However, since DSC uses an electrolytic solution, there are problems of leakage of the electrolytic solution and short circuit. Further, the photoelectric conversion efficiency is lower than that of silicon-based solar cells, and further improvements are being studied.
For example, in order to increase the photoelectric conversion efficiency as much as possible, when a working electrode is provided on the light incident side, a transparent conductive film made of ITO or FTO used for the working electrode has a high resistance value. The use of is being considered.
Patent Document 1 proposes a network electrode having a net-like conductive body made of a metal wire such as platinum as a core and entirely covered with a porous oxide semiconductor layer.
Patent Document 2 proposes a photoelectric conversion element in which a semiconductor fine particle layer is laminated on one side of a metal net such as expanded metal.

In recent years, there has been a problem that the reinforcing bars in concrete such as bridges rust and the concrete peels off. As a countermeasure against this, anti-corrosion is known to reduce the potential of the reinforcing bar to a potential that does not corrode by passing an electric current from an electrode placed on the concrete surface to a steel material such as a reinforcing bar in the concrete, thereby suppressing the progress of corrosion. .
Conventionally, as an electron supply body used for cathodic protection, one has an external power source such as a commercial power source, and the other is a base metal such as zinc, magnesium, and aluminum whose oxidation-reduction potential is lower than that of the body to be protected. And galvanic anodes (sacrificial anodes) made of these alloys.
However, the external power source has problems such as that it takes time to install an auxiliary electrode such as a titanium mesh, that it is difficult to secure a commercial power source, and that it is necessary to maintain and manage the power source. Moreover, there is a problem that the galvanic anode is consumed over time.

In recent years, an anticorrosion using a titanium oxide film as an electron supplier has been proposed for such problems.
For example, in Patent Document 3, electrons generated when light strikes a titanium oxide film provided on a support such as a metal plate or a plastic film are injected into the metal to be protected through a conductive wire, thereby preventing the corrosion. It is supposed to be possible.
And in patent document 4, it is supposed that the electron which generate | occur | produces when light strikes a titanium oxide film can be corroded by collecting with a conductive film and inject | pouring into an anticorrosion object metal.

An optical sensor using titanium oxide is also known for measuring light in a specific wavelength region such as ultraviolet light.
For example, in Patent Document 5, an electrolyte solution is sealed between a working electrode in which titanium oxide is applied to a conductive surface of a transparent conductive glass to adsorb a two-photon absorption dye and a counter electrode made of conductive glass on which platinum is deposited. An optical sensor has been proposed.
In Patent Document 6, titanium oxide is accumulated in the porous aluminum oxide film of the anodized aluminum plate, and the titanium oxide layer is brought into contact with the transparent electrode provided on the transparent conductive glass. There has been proposed an optical sensor comprising a working electrode in contact with the electrode, a charge transfer layer made of an aluminum oxide film, and an aluminum plate. Patent Document 6 describes a conventional optical sensor having a structure in which an electrolyte solution is sealed between a working electrode obtained by applying titanium oxide on the conductive surface side of a transparent conductive glass and a counter electrode made of conductive glass. Yes.

JP 2001-283944 A JP 2007-73505 A JP 2001-234370 A JP 2001-262379 A JP 2001-210857 A JP-A-11-220158

However, in the DSC proposals of Patent Documents 1 and 2 using a metal network as the conductive layer, the electrolyte is used in a solution state, and therefore the electrolyte can be brought into contact with titanium oxide irradiated with light on the front side. Since the metal cannot be wrapped around the metal net, it cannot be brought into contact with the titanium oxide irradiated with the light on the front side. Therefore, it must be assumed that the electrolyte is used in a solution state.
By the way, in the proposals of Patent Documents 1 and 2, it is said that a liquid electrolyte may be contained in a polymer substance or gelled with a low molecular gelling agent. However, there is no disclosure at all about a specific configuration in which the electrolytic solution is brought into contact with the titanium oxide irradiated with light by wrapping around the metal net. Further, there is no detailed disclosure of a method for containing a liquid electrolyte in a polymer substance or gelling with a low molecular gelling agent.
When using an electrolyte solution, there is a problem of leakage of the electrolyte solution. In addition, the conductive layer and the counter electrode are easily short-circuited, and in the proposals of Patent Documents 1 and 2, the installation of an insulating layer for preventing a short circuit is recommended. In the case where an insulating layer is not provided, it is necessary to provide a spacer.
In addition, the method for producing the metal net or the metal layer is complicated, and the metal having good corrosion resistance against the electrolyte solution is often expensive, which may increase the production cost.

In Patent Document 1, an embodiment in which a metal net is completely embedded in a titanium oxide layer is illustrated. In this embodiment, even when the solidified electrolyte is used, it is estimated that photoelectric conversion is possible because the titanium oxide on the back side of the metal mesh contacts the electrolyte. However, since titanium oxide that is not exposed to light is substantially an insulator, titanium oxide irradiated with light on the front side is not effectively utilized unless a large amount of electrolyte penetrates into the titanium oxide layer. Therefore, the titanium oxide on the back side of the metal net is not only wasted, but as shown in Example 1 and Comparative Example 2 of Patent Document 2, the titanium oxide on the back side of the metal net hinders ion transmission, rather, photoelectric conversion. Efficiency may be reduced.
Therefore, the proposal of Patent Document 1 uses a plurality of network electrodes to irradiate the back side titanium oxide layer with reflected light. In order to bring the electrolyte into contact with the plurality of network electrodes, it is necessary to use the electrolyte in a solution state, and it is impossible to solidify the electrolyte.

Moreover, since the method and apparatus of patent documents 3 and 4 in the electron supply body of an anticorrosion use a conductive wire and a conductive film, it seems that it is possible to inject | pour an electron into metals, such as a rebar embed | buried in concrete.
However, the anticorrosion circuit shown in Patent Documents 3 and 4 has a circuit configuration of titanium oxide film-conductive wire-corroded body. This circuit is not a circuit closed by an auxiliary anode like a normal external power supply type anticorrosion circuit. In such a circuit configuration on only one side, an auxiliary anode in an external power supply system that transports positive charges generated when titanium oxide emits electrons to the body to be corroded by ionic conductivity and reduces it by the electrons of the body to be corroded. Since there is no such means, the electric current generated by the electrons generated from the titanium oxide film cannot be obtained, so that the potential of the corrosion-protected body cannot be reduced.

  Further, the inventions of Patent Documents 5 and 6 and the prior art of Patent Document 6 for optical sensors apply the DSC operating principle and have the same problems as DSC. In particular, the prior art disclosed in Patent Document 6 has the above-described problems associated with the electrolyte solution. For such a problem, a solid charge transfer layer can also be used in the optical sensor. However, since a transparent conductive substrate in which a transparent conductive film is laminated on a transparent glass plate or the like is also used, high photoelectric conversion efficiency cannot be expected. Therefore, it may be a problem when high sensitivity is required. When an organic hole transport layer such as aromatic amines, a conductive polymer layer such as polyaniline, or a charge transfer layer such as a p-type inorganic compound semiconductor is used instead of the electrolyte, the contact with the semiconductor layer is poor. As a result, the photoelectric conversion efficiency further decreases.

  The present invention has been made in view of the above circumstances, in which there is no leakage of an electrolyte solution, excellent handleability, easy manufacturing using an inexpensive material, and a transparent conductive film such as ITO is not preferable. Even if it exists, it makes it a subject to provide the electron supply body which can supply sufficient electrons.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, when collecting electrons emitted from a semiconductor by electromagnetic waves as a working electrode, the conductive material mainly composed of carbon is used as a fiber substrate or film. Current is collected using a conductive layer made of a conductive base material coated and / or impregnated with a substance, supplied to the counter electrode, and solidified to transport charge from the semiconductor layer as charge transfer due to ionic conductivity The idea was to provide an electrolyte layer. And, there is no leakage of the electrolyte solution, no short circuit with the counter electrode, excellent handleability, using an inexpensive material, easy to manufacture, even when a transparent conductive film such as ITO is not preferable, The present invention has been completed by obtaining knowledge that an electron supplier capable of supplying sufficient electrons can be provided.

  That is, the present invention relates to a solidified sheet-like first electrolyte layer, and a conductive group obtained by applying and / or impregnating a conductive material containing carbon as a main component to a fiber substrate and / or a film substrate. A conductive layer made of a material, a semiconductor layer that generates electrons by electromagnetic waves, and a solidified sheet-like second electrolyte layer that can transmit electromagnetic waves in this order, the second electrolyte layer, Provided is an electron supply body formed so as to be capable of transferring electric charge by contact or approach with the first electrolyte layer.

In the present invention, the conductive layer is a fiber substrate made of woven or non-woven fabric, and charge transfer between the first electrolyte layer and the second electrolyte layer is enabled by ion permeability in the gaps between the fibers. It is preferable.
In addition, it is preferable that a plurality of holes that allow ions to pass therethrough are formed in the conductive layer so that charges can be transferred between the first electrolyte layer and the second electrolyte layer.
It is preferable that both the first and second electrolyte layers are conductive hydrogels in which an electrolyte salt is contained in a hydrogel having at least water in a hydrophilic resin matrix.

Further, at least a part of the peripheral portions of the first electrolyte layer and the second electrolyte layer is extended from the periphery of the conductive layer and the semiconductor layer, and the peripheral portions are in contact with each other, and these electrolyte layers are in contact with each other. It is preferable that a contact portion in which the electrolyte can move is formed.
It is preferable that the conductive layer is capable of charge transfer between the first electrolyte layer and the second electrolyte layer.
Furthermore, it is preferable that a protective layer capable of transmitting electromagnetic waves is disposed on the semiconductor layer or the second electrolyte layer.

Further, it is preferable that the protective layer or both the protective layer and the second electrolyte layer can transmit electromagnetic waves having a wavelength of at least 340 nm to 500 nm.
The semiconductor layer is preferably a layer containing one or more metal oxides selected from titanium oxide, zinc oxide and tin oxide.
It is preferable that the electron supply body is used for an anticorrosion structure, a dye-sensitized solar cell, or an optical sensor.

  According to the invention of claim 1, when collecting electrons generated in the semiconductor layer by electromagnetic waves as a working electrode, the conductive base material is coated and / or impregnated with a conductive material mainly composed of carbon. Therefore, it is cheaper than using noble metals such as platinum and gold as the conductive material, and it has better chemical stability and is incorporated in the circuit than when using a base metal such as zinc as the conductive material. Durability against corrosion over time associated with the generation of current at the time is high. Moreover, since these materials can be applied and / or impregnated with a general-purpose coating apparatus, they are easy to manufacture. Therefore, while being an inexpensive material, it has excellent conductivity and high corrosion resistance to the electrolyte solution.

Further, by providing the first electrolyte layer and the second electrolyte layer, the positive charge generated when the semiconductor emits electrons is efficiently transported to the counter electrode of the circuit or the corrosion-protected body of the corrosion-proof structure by ionic conductivity. be able to. Thereby, since it reduces by the counter electrode and the to-be-protected body to which the electron was supplied, an electric current can be obtained reliably.
And since any electrolyte layer is solidified, there is no leakage of the electrolyte, and for example, it can be directly laminated on the counter electrode of the dye-sensitized solar cell or the photosensor or the corrosion-protected body, and the short circuit with the counter electrode is also possible. Absent.
Therefore, since it is excellent in handleability, can be easily manufactured, and can be configured without using a transparent conductive film such as ITO, an electron supply body excellent in photoelectric conversion efficiency, cost, and durability can be provided.

According to invention of Claim 2, since the thickness of a conductive layer and the micro clearance gap between fibers can be adjusted easily, the ion permeability of a conductive layer can be controlled easily.
In addition, since a conductive layer having a large surface area per unit volume can be formed, the conductivity can be easily controlled.
According to the third aspect of the present invention, since the holes provided in the conductive layer enable the movement of electric charge between the first electrolyte layer and the second electrolyte layer, the first contact with the semiconductor layer over a large area is possible. Charges can be efficiently transported from the semiconductor layer by the two electrolyte layers.

  According to the invention of claim 4, since the conductive hydrogel can easily impart flexibility and adhesiveness, the first and second electrolyte layers are adhered to the conductive layer and the semiconductor layer with good adhesion. be able to. Moreover, when the counter electrode of a circuit which requires an electron supply body, or an electron supply body is used for an anticorrosion structure, it can adhere to a concrete layer etc. with sufficient adhesiveness.

  According to the invention of claim 5, the charge can move between the first electrolyte layer and the second electrolyte layer through the contact portion between the peripheral portions of the electrolyte layer, and the contact area with the semiconductor layer is large. Charges can be efficiently transferred from the semiconductor layer through the second electrolyte layer.

  According to the invention of claim 6, it is possible to prevent the semiconductor layer and the second electrolyte layer from being exposed to wind and rain, etc., and being damaged or contaminated, thereby improving the performance of the electron supply body for a longer period of time. Can be maintained over time. In addition, when the second electrolyte layer is a conductive hydrogel, drying and swelling of the hydrogel can be prevented.

  According to the seventh aspect of the invention, when titanium oxide or sensitized titanium oxide is used as the semiconductor for forming the semiconductor layer, it is possible to effectively use light having a short wavelength contained in sunlight or the like. .

  According to the invention of claim 8, even if the incidence of electromagnetic waves is weak, a large amount of electrons can be emitted and supplied to the circuit.

It is sectional drawing which shows typically the 1st form example of the electron supply body of this invention. It is sectional drawing which shows typically the 2nd form example of the electron supply body of this invention. It is sectional drawing which shows typically the 3rd example of an electron supply body of this invention. It is sectional drawing which shows typically the 4th form example as the comparative example 1 of an electron supply body. It is sectional drawing which shows typically an example of the anticorrosion structure which used the electron supply body of this invention as a working electrode of an anticorrosion. It is sectional drawing which shows typically another example of the anticorrosion structure which used the electron supply body of this invention as a working electrode of an anticorrosion. (A) And (b) is sectional drawing which shows an example of a hole typically. (A) And (b) is a top view which shows an example of a hole typically. It is a graph which shows the IV curve in Examples 1-3 and the comparative example 1 of an electron supply body. It is sectional drawing which shows typically the structure of the comparative example 2 of an electron supply body. It is sectional drawing which shows typically the structure of the comparative example 3 of an electron supply body. It is typical sectional drawing which shows the test method of the anticorrosion structure using the electron supply body of Examples 4-7 of this invention. It is a graph which shows an example of the test result of the reinforcing bar electric potential of the anticorrosion structure using Example 4 of the electron supply body of this invention. It is a graph which shows an example of the test result of the reinforcing bar electric potential of the anticorrosion structure using Example 5 of the electron supplier of the present invention. It is a graph which shows an example of the test result of the reinforcing bar electric potential of the anticorrosion structure using Example 6 of the electron supplier of the present invention. It is a graph which shows an example of the test result of the reinforcing bar potential of the anticorrosion structure using Example 7 of the electron supply body of the present invention. It is a graph which shows an example of the test result of the generated current density of the anticorrosion structure using Example 4 of the electron supply body of the present invention. It is a graph which shows an example of the test result of the generated current density of the anticorrosion structure using Example 5 of the electron supply body of the present invention. It is a graph which shows an example of the test result of the generated current density of the anticorrosion structure using Example 6 of the electron supply body of this invention. It is a graph which shows an example of the test result of the generated current density of the anticorrosion structure using Example 7 of the electron supply body of this invention.

The present invention will be described below based on preferred embodiments with reference to the drawings.
FIG. 1 schematically shows an electron supply body 10 as a first embodiment of the electron supply body of the present invention, and FIG. 5 schematically shows an example of an anticorrosion structure 20 using the electron supply body 10 as a working electrode for anticorrosion. . As will be described in detail later, the electron supply body of the present invention transfers the positive charge of the semiconductor layer 12 generated as a result of the emission of electrons to the anticorrosive body 22 serving as the counter electrode by ionic conductivity, thereby supplying the electron supply body 10. The charge transfer means for reducing with the electrons of the to-be-protected body 22 supplied from is formed on the electron supply body itself.
Note that ionic conductivity refers to energization by ions, and includes cases where ions move due to diffusion or the like and charges are transported, and cases where charges move between ions due to a potential gradient or the like.

  The electron supply body 10 of this embodiment has a conductive layer 11 that collects electrons. A semiconductor layer 12 that emits electrons by electromagnetic waves is formed on one surface of the conductive layer 11. Since the conductive layer 11 is in close contact with the semiconductor layer 12, electrons generated in the semiconductor layer 12 can be efficiently transferred to the conductive layer 11. The semiconductor layer 12 and the conductive layer 11 are preferably in close contact with the conductive layer 11 because the entire surface of the semiconductor layer 12 is in close contact with the conductive layer 11. Moreover, although mentioned later for details, the part which the semiconductor layer of the conductive layer 11 is not closely_contact | adhered can be utilized as an extraction electrode of an electron.

Further, on the other surface of the conductive layer 11, a first electrolyte layer 13 having an electrolyte in a solid is formed in a layer shape.
The first electrolyte layer 13 transports positive charges received by the second electrolyte layer 14 from the semiconductor from which electrons have been emitted, to the corrosion-protected body 22 by ionic conductivity of the surface layer 21 such as a concrete layer. The transported positive charge is reduced by the electrons supplied from the electron supply body 10 to the corrosion-protected body 22. That is, the first electrolyte layer 13 serves as an auxiliary anode that transports positive charges to the corrosion-protected body 22 via the surface layer 21.
Also, it plays a role of fixing the electron supply body 10 to the surface layer 21 of the body to be protected 22.
Therefore, it is preferable that the first electrolyte layer 13 is equal to or wider than the conductive layer 11, and stickiness or adhesiveness (hereinafter referred to as “adhesion” without distinguishing between “adhesion” and “adhesion”). The conductive hydrogel is preferably made of a conductive hydrogel having excellent conformability to unevenness. From the viewpoint of fixing the electron supply body 10, the first electrolyte layer 13 is preferably made of a conductive hydrogel excellent in followability to unevenness.

Furthermore, on the semiconductor layer 12, a second electrolyte layer 14 having an electrolyte in a solid is formed in a layer shape. The second electrolyte layer 14 serves to receive the positive charge of the semiconductor that has emitted electrons. The second electrolyte layer 14 is capable of transmitting electromagnetic waves so as not to prevent the electromagnetic waves from entering the semiconductor layer 12. When titanium oxide or sensitized titanium oxide is used as the semiconductor for forming the semiconductor layer 12, the second electrolyte layer 14 has a wavelength of at least 340 nm to 500 nm in order to effectively use a short wavelength light beam. It is preferable that the electromagnetic wave in the region can be transmitted.
The second electrolyte layer 14 is preferably about the same as or wider than the semiconductor layer 12, and is preferably made of a conductive hydrogel excellent in conformity to unevenness.

The electron supply body 10 according to the present embodiment connects the conductive layer 11 to the corrosion-protected body 22 via the circuit wiring 23 as in the anticorrosion structure 20 shown in FIG. The anticorrosion circuit is formed by being attached to 21 and electrically connected with ion conductivity.
In this anticorrosion circuit, electrons generated in the semiconductor layer 12 are collected by the conductive layer 11 and supplied to the anticorrosive body 22. On the other hand, this anticorrosion circuit covers positive charges generated in the semiconductor layer 12 due to electron emission by the ionic conductivity of the first electrolyte layer 13 and the second electrolyte layer 14 and the ionic conductivity of the concrete layer 21. It moves to the corrosion protection body 22 and is reduced by the electrons of the corrosion protection body 22.
That is, the anticorrosion structure 20 of FIG. 5 includes the semiconductor layer 12 -the conductive layer 11 -the circuit wiring 23 -the corrosion protection object 22 and the charge transfer path by electrons, the semiconductor layer 12 -the second electrolyte layer 14 -the first electrolyte. It consists of the charge transfer path by the ionic conductivity of layer 13-concrete layer 21-corroded body 22.
And since it is reduce | restored by an electron in the to-be-protected body 22, it becomes an electrically connected closed circuit. Thereby, even if it is a case where the electron production amount of the semiconductor layer 12 is small, an electric current can be sent through the to-be-protected body 22 and a potential can be made into a base.

The electron supply body 10 of this embodiment is installed in a place where electromagnetic waves are incident. Such a place may be a place where sunlight or the like directly shines. However, in the present invention, since a high anticorrosion effect can be obtained even with the generation of a small amount of electrons, the shade such as the wall where the structure is not exposed to the sun and the lower surface of the bridge. Can also be installed. In particular, the underpass of an elevated road or a bridge is preferable because it is not directly exposed to rain, so that the electrolyte layers 13 and 14 do not swell and the electrolyte does not elute.
When the electron supply body 10 is installed in water or in a place where it is intermittently flooded, a protective layer 17 is provided on the light receiving surface of the electron supply body 10 as shown in FIG. It is preferable that a waterproof treatment is performed so as to prevent water from entering the semiconductor layer 12 and the electrolyte layers 13 and 14 by covering with an impermeable resin layer having excellent weather resistance such as epoxy or acrylic. By performing waterproofing in this way, corrosion prevention is possible by sticking the electron supply body 10 in the vicinity of the boundary between seawater and air, which is said to be most corrosive in metals that touch seawater. Further, corrosion prevention can be similarly applied to reinforcing bars and the like in concrete structures in a similar environment.

As a conductor constituting the circuit wiring 23, a normal metal conductor such as copper or aluminum can be used. The circuit wiring 23 is preferably covered with a synthetic resin, enamel or the like on a metal conductor for protection and insulation. The circuit wiring 23 may be fixed to the electron supply body 10 in advance, or may be fixed to the electron supply body 10 at a construction site. The method of fixing at the construction site is preferable because it is easy to match the situation at the construction site.
In addition, since the electron supply body 10 has a relatively thin shape such as a film, a sheet, and a plate, when storing or transporting a plurality, the electron supply body 10 may be overlapped with a single sheet or in a long state. It may be wound on a roll.

Hereinafter, main members constituting the electron supply body 10 of this embodiment will be described in detail.
<< Conductive layer 11 >>
The conductive layer 11 is a conductive layer that collects electrons generated in the semiconductor layer 12 by electromagnetic waves. If the conductive layer 11 is conductive, it is ion-impermeable such as a metal foil, a conductive polymer layer, a film in which a thin film of a conductive substance such as carbon, metal, or metal oxide is laminated by coating or vapor deposition. Any ion-permeable conductive fiber substrate layer formed by forming a fiber substrate such as a layer, woven fabric, nonwoven fabric, knitted fabric, or paper into a thin film can be used.
Among these, the metal foil is preferable because it is excellent in conductivity, but it may be corroded by an electrolyte solution (electrolytic solution), so it is necessary to use gold, platinum or titanium, which is disadvantageous in terms of cost. Further, the conductive polymer layer has a drawback that it is difficult to obtain high conductivity. Therefore, it is preferable that the conductive layer 11 is a layer obtained by applying and / or impregnating a base material with a paste-like conductive material, because it is advantageous in terms of conductivity and cost.

  Here, the application means that the conductive material is mainly attached to the surface of the base material, and the impregnation means that the conductive material is attached to the surface of the base material and penetrates into the inside. Need not be interpreted in a particularly strict manner. In short, it is only necessary that the conductive material adheres to the substrate at least on the surface thereof to a practically sufficient extent, and the conductive material does not necessarily penetrate into the substrate. However, in the case of a fiber base material, since the conductivity of the conductive layer 11 is high, it is preferable that the conductive material penetrates into the base material. Hereinafter, it may be expressed as “application” including impregnation.

  When the base material used for applying the conductive material is a fiber base material, when applying the conductive material, the conductive layer 11 is applied so that a minute gap is formed between the fibers and the conductive layer 11 is ion-permeable conductive fiber base. It can be a material. As a result, the second electrolyte layer 14 that receives the positive charge generated in the semiconductor layer as a result of generation of electrons and the first electrolyte layer 13 conduct with ionic conductivity, so that the positive charge is efficiently transferred from the semiconductor layer 12. Can be moved.

It is preferable to use the conductive layer 11 as the conductive fiber base because the contact area with the semiconductor layer 12 and the first electrolyte layer 13 is increased due to the unevenness on the surface of the fiber base. And when using the electrolyte layer which has adhesiveness in the 1st electrolyte layer 13, and is flexible and is excellent in the followable | trackability with an unevenness | corrugation, the part of conductive hydrogel is a fiber base material. It penetrates into the gap and the adhesion is increased, so that positive charges can be efficiently moved to the corrosion-protected body 22.
In addition, since the conductive fiber base material can have high conductivity by increasing the surface area per unit volume, it is easy to control conductivity and ion permeability.

Non-conductive fibers such as glass fibers, animal fibers, vegetable fibers, synthetic fibers such as polyester (PET) and polyamide are woven fabrics, non-woven fabrics, and knitted fabrics. A fiber base material processed into a thin film such as cloth or paper may be provided with conductivity, and a conductive fiber such as metal fiber such as copper or nickel, or carbon fiber, or a thin film such as woven fabric, non-woven fabric, knitted fabric or paper. The fiber base material processed into may be used.
A fiber base made of metal fibers is excellent in conductivity, but may corrode over time with the generation of an electrolyte solution or current. In such a case, it is preferable to apply, for example, a carbon-based conductive material having excellent corrosion resistance, even if the fiber base material is made of a conductor. In this case, since the whole fiber base material becomes conductive, high conductivity can be expected.

Among these fiber base materials, a woven fabric is preferable because a conductive material can be applied smoothly, and thus it is easy to form the semiconductor layer 12 on the conductive layer 11. From this viewpoint, taffeta made of PET, polyamide or the like having excellent smoothness is preferable.
Nonwoven fabrics are preferable because the thickness of the conductive layer 11 and the minute gaps of the fibers can be easily adjusted, and the ion permeability and conductivity can be easily controlled.
Examples of the method for producing the nonwoven fabric include a method in which a fleece produced by a dry method, a wet method, a spun bond method, a melt blow method or the like is bonded by a known method such as a thermal bond method or a spun lace method.
The thickness of the conductive layer 11 made of the conductive fiber base material is not limited as long as the conductivity is ensured, but is usually preferably about 20 μm to 200 μm. If it is thinner than this range, the conductivity and physical strength may be insufficient. Moreover, when it is thick, ion permeability may fall.

The conductive layer 11 may be made of a conductive base material obtained by applying and / or impregnating a conductive material to a film.
It is preferable that the base material used for applying the conductive material is a film, since it can be applied uniformly and accurately when the conductive material is applied. Moreover, since a conductive substance does not permeate | transmit the back side of a film, it can apply | coat with a general purpose simple coating apparatus. However, when the substrate is a film, it may be difficult to apply the conductive material thickly. In such a case, a conductive substance may be applied to both sides of the film. In this case, it is preferable to make the conductive material layers on the front and back conductive by making the film porous or connecting the front and back with a conductive tape. Further, the conductive material layer may be reinforced by embedding the fiber base material in the conductive material layer or by blending short fibers in the conductive material.
The thickness of the film used for the conductive layer 11 is not limited as long as the physical strength is ensured, but can usually be about 10 μm to 100 μm.

  There is no restriction | limiting in particular as a film used for the conductive layer 11, Although metal foil may be sufficient, since it is excellent in corrosion resistance, the film which consists of synthetic resins is preferable. Examples of the resin forming the film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); fluorine resins such as polytetrafluoroethylene (PTFE) and ethylene-tetrafluoroethylene copolymer (ETFE): Acrylic resins; Polyolefin resins such as polyethylene and polypropylene; Polyamide resins such as nylon; Tetraacetyl cellulose (TAC); Polyester sulfone (PES); Polyphenylene sulfide (PPS); Polycarbonate (PC); Polyarylate (PAr); Polysulfone (PSF); Polyetherimide (PEI); Polyacetal; Polyimide polymer; Polyethersulfone and the like.

The conductive material applied to the substrate can be nickel, zinc, copper, or other metal powder, but it is inexpensive and has excellent durability (corrosion resistance) against electrolyte solutions. Material is preferred. Of the carbon-based materials, those containing conductive carbon as a main component are more preferable. Note that “main component” means that the composition ratio is 50% or more, and may be 100%.
Examples of the conductive carbon include graphite; various carbon blacks such as ketjen black, thermal black, acetylene black, channel black, and furnace black; carbon nanotubes and the like. Of these, graphite, ketjen black, and carbon nanotubes are preferable because of their high conductivity, and graphite that is inexpensive and has high conductivity is particularly preferable.
By using a carbon-based material as the conductive material, it is cheaper than when noble metals such as platinum or gold are used as the conductive material, and chemically stable compared to when using a base metal such as nickel or zinc as the conductive material. In addition, the durability against corrosion over time associated with the generation of an electrolyte solution or current can be increased.

  As a method of applying the conductive material to the fiber base material or film, for example, the conductive material powder or short fibers are dispersed in an organic solvent or the like to form a paste, and the obtained conductive paste is applied to, for example, a gravure coat, a bar Examples thereof include a method of drying after coating by a coating method such as coating or screen coating. In order to improve the dispersibility of the conductive material, additives such as a dispersant may be added to the conductive paste.

When the application amount of the conductive material is increased in order to increase the conductivity of the conductive layer 11, a minute gap in the fiber base material may be clogged with the conductive material. Alternatively, there is a case where a conductive material is applied to the film base material and it is desired to impart ion permeability. In such a case, it is preferable to provide a plurality of holes 18 as shown in FIGS. 7 and 8 to ensure ion permeability. When the hole 18 is formed, the function of the second electrolyte layer 14 for diffusing ions in the horizontal direction is effectively exhibited, and the charge transfer to the first electrolyte layer 13 becomes smooth.
FIG. 7A shows an example in which the hole 18 penetrates the conductive layer 11 and contacts the back surface of the semiconductor layer 12, and FIG. 7B shows the hole 18 between the conductive layer 11 and the semiconductor layer 12. The example which has penetrated both is shown.

  In the case of FIG. 7A, the hole 18 is not formed in the semiconductor layer 12, and the contact portion 18 a with the semiconductor layer 12 is formed on the top surface of the hole 18. The charge transfer to one electrolyte layer 13 depends on the ion permeability of the semiconductor layer 12. In this case, the charge transfer is also smooth between the first electrolyte layer 13 and the semiconductor layer 12. This aspect is preferable when the semiconductor layer 12 is formed after the conductive layer 11 is perforated. Moreover, since the 1st electrolyte layer 13 contacts the semiconductor layer 12 directly, it is preferable also when the 2nd electrolyte layer 14 does not exist (refer FIG. 4).

  In the case of FIG. 7B, the contact portion 18 b between the first electrolyte layer 13 and the second electrolyte layer 14 is formed inside the hole 18, and the hole 18 is formed in the semiconductor layer 12. The first electrolyte layer 13 and the second electrolyte layer 14 are in direct contact with each other so that charge transfer is possible. Also in this case, the charge can directly move between the first electrolyte layer 13 and the semiconductor layer 12. This aspect is preferable when the conductive layer 11 is perforated after the semiconductor layer 12 is formed.

The inner diameter of the hole 18 may be small as long as ion permeation is possible. However, since it is preferable that a part of the electrolyte layers 13 and 14 enter the hole 18 and directly contact them, for example, 0.3 When the size is about 10 mm or so and the thickness of the conductive layer 11 is large, the diameter of the hole 18 is preferably relatively large.
In addition, when the electrolyte layers 13 and 14 are electroconductive hydrogels containing electrolyte solution (electrolyte solution), the movement of electric charge is possible if the electrolyte solution exuded from the electroconductive hydrogel is filled in the holes 18. Therefore, the first electrolyte layer 13 is not necessarily in direct contact with the semiconductor layer 12 or the second electrolyte layer 14 in the hole 18.

  FIG. 8 is a plan view of the conductive layer 11 in which the holes 18 are formed. FIG. 8A shows an example in which the holes 18 are aligned perpendicularly or parallel to the sides of the conductive layer 11, and FIG. In this example, 18 are arranged obliquely along the sides of the conductive layer 11. The arrangement of the holes 18 may be irregular, but when the adjacent holes 18 form a polygon such as a triangle, a square, a rectangle, a rhombus, and a hexagon to form a regular arrangement, the holes 18 are arranged. This is preferable because the charge moves more evenly.

  The hole 18 can be formed by a known method such as punching, laser beam, drilling using a hot needle or a cold needle. Punching with a punch or a laser beam provides a hole having a relatively large diameter compared to drilling with a hot needle or cold needle, and the first electrolyte layer 13 is in direct contact with the semiconductor layer 12 or the second electrolyte layer 14. It becomes easy to do. The perforation using the cold needle is in a state in which the periphery of the hole 18 is irregularly cleaved, and it is difficult to form a clear hole. However, when conductive hydrogel is used, the permeation of ions from the crevice gap is prevented. Is possible. In the melt drilling using a laser beam or a hot needle, the periphery of the hole 18 is melted and solidified to form a clear hole, and even if the holes 18 are provided at a high density, the strength reduction of the conductive layer 11 is relatively small.

The shape of the hole 18 is not particularly limited, and may be a circle, an ellipse, a square, a rectangle, a polygon, an indeterminate shape, or any other shape.
The hole 18 does not necessarily need to be an independent hole whose entire periphery is surrounded by the conductive layer 11, and may be a notch or a simple groove with a part of the periphery open. When the shape of the groove is adopted, it is preferable to connect the conductive layer 11 divided by the groove when collecting the current collected by the conductive layer 11 using a conductor such as copper or aluminum.
Such formation of the holes 18 can be preferably applied to the case where the conductive layer 11 is provided with ion permeability in the case of using a film in which a metal foil, a conductive polymer layer, or a thin film layer of a conductive substance is laminated. .

<< Semiconductor layer 12 >>
The semiconductor layer 12 is a layer that emits electrons in response to electromagnetic waves.
The semiconductor material for forming the semiconductor layer 12 is not particularly limited as long as it can emit electrons upon receiving electromagnetic waves. For example, a single semiconductor such as silicon and germanium, a metal oxide, and a metal chalcogenide (for example, sulfide) And so-called compound semiconductors such as selenides, etc., or compounds having a perovskite structure such as strontium titanate can be used.
Examples of these oxide and chalcogenide metals include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium, zinc, lead, Silver, antimony or bismuth sulfide, cadmium or lead selenide, cadmium telluride and the like.

Examples of the compound semiconductor include phosphides such as zinc, gallium, indium, and cadmium, gallium arsenide, copper-indium selenide, copper-indium-sulfide, and the like. There are n-type semiconductors in which the carrier involved in charge transfer is an electron and p-type in which the carrier is a hole. In the present invention, the n-type is preferably used.
Examples of such n-type inorganic semiconductors include TiO ₂ , TiSrO ₃ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , Si, CdS, CdSe, V ₂ O ₅ , ZnS, ZnSe, SnSe, KTa ₃ , _{FeS 2, PbS, InP, GaAs} , there is such as CuInS _2, CuInSe 2. Of these semiconductors, titanium oxide (TiO ₂ ), zinc oxide (ZnO), and tin oxide (SnO ₂ ) are preferable.

Of these semiconductors, titanium oxide is more preferable because it has an excellent ability to emit electrons upon receiving electromagnetic waves. Of the titanium oxides, anatase-type titanium oxide or brookite-type titanium oxide is preferable because of its excellent ability to emit electrons upon receiving electromagnetic waves, and anatase-type titanium oxide is particularly preferable because of its excellent versatility. These semiconductors may be used singly or as a mixture of two or more if necessary. The anatase type titanium oxide and brookite type titanium oxide are not limited to anatase and brookite as natural minerals, and may be artificially synthesized.
Since the semiconductor layer 12 is in contact with the electrolyte solution of the first electrolyte layer 13 and the second electrolyte layer 14, a porous film made of semiconductor fine particles is preferable because the contact area increases. The particle diameter of the semiconductor fine particles is preferably such that the average particle diameter of primary particles obtained from the diameter when the projected area is converted into a circle is 5 to 200 nm.

The semiconductor layer 12 is formed by a known method such as a coating method in which a dispersion or colloidal solution of semiconductor fine particles is applied on the conductive layer 11, a sol-gel method using titanium alkoxide, or a method in which titanium chloride is hydrolyzed. Can be adopted. Among these, the coating method is preferable from the viewpoint of production efficiency. Examples of the coating method include coating methods such as gravure coating, bar coating, and screen coating.
The semiconductor layer 12 can use a sensitizer such as a sensitizing dye in order to sensitize the semiconductor. Examples of the sensitizing dye include organometallic complex dyes, porphyrin dyes, phthalocyanine dyes, methine dyes, and the like. These dyes are used for the purpose of expanding the wavelength range, controlling to a specific wavelength range, and the like. These dyes may be used alone or in combination of two or more as required.

≪Electrolyte layers 13 and 14≫
The electrolyte layers 13 and 14 are charge transfer layers solidified in a sheet shape having an electrolyte salt for ionic conductivity. Electrolyte layers 13 and 14 contain positive and negative ions, and these ions move or electric charges move between these ions, thereby electrically connecting the circuits. Therefore, the generation of reverse current can be prevented or suppressed. The electrolyte layers 13 and 14 may have different electrolyte salts, but it is preferable to have the same electrolyte salt because the movement of ions becomes smooth.
Examples of main electrolytes that can be used for the electrolyte layers 13 and 14 include gel electrolytes in which an electrolytic solution is held in a resin matrix, molten salt electrolytes, solid electrolytes using zirconia, and the like. The electrolyte layers 13 and 14 may be different types of electrolyte layers. However, it is preferable that the electrolyte layers 13 and 14 are the same electrolyte layer because the movement of electric charges becomes smooth.
Of these, the gel electrolyte is preferable because it is rich in flexibility. The gel electrolyte is obtained by gelling (solidifying) an electrolyte by adding a polymer, adding an oil gelling agent, polymerization containing polyfunctional monomers, a crosslinking reaction of the polymer, or the like.
A conductive water-containing gel (conductive hydrogel) in which water and an electrolyte salt are held in a hydrophilic resin matrix in a gel electrolyte, the charge transfer speed is fast, and flexibility and tackiness are easily achieved. Since it can provide, it is more preferable.

The first electrolyte layer 13 adheres the electron supply body 10 to the ion-permeable surface layer 21 existing on the surface of the corrosion-resistant body 22 and also from the semiconductor layer 12 via the second electrolyte layer 14. 22 is a layer for transporting electric charges to 22. When the first electrolyte layer 13 is a conductive hydrogel that becomes a flexible pressure-sensitive adhesive layer, when the electron supply body 10 is attached to the surface layer of the corrosion-protected body 22, for example, the concrete layer 21, It is preferable because a part of the electrolyte layer enters the minute unevenness, and the electrolyte layer can be brought into contact and bonded with high adhesive strength and a wide contact area. The first electrolyte layer 13 may be transparent or opaque.
In addition, since the conductive hydrogel used for the first electrolyte layer 13 has a resin matrix, the conductive layer 11 does not come into contact with the metal even if the electron supply body 10 is directly bonded to the surface of the metal serving as the corrosion protection body. So there is no short circuit. From the viewpoint of preventing a short circuit, the thickness of the conductive hydrogel used for the first electrolyte layer 13 is preferably 100 μm to 1000 μm. Further, a reinforcing material such as a woven fabric or a non-woven fabric may be placed in the conductive hydrogel.
And since electroconductive hydrogel has water retention, it also has a function which prevents that the dry degree of the concrete layer 21 becomes high and the electric charge in the concrete layer 21 becomes difficult to move.

  The second electrolyte layer 14 is a layer that is stacked on the semiconductor layer 12 and moves charges from the semiconductor layer 12 by ionic conductivity. When the second electrolyte layer 14 is a conductive hydrogel that becomes a flexible pressure-sensitive adhesive layer, a part of the second electrolyte layer 14 penetrates into the minute irregularities of the semiconductor layer 12 when laminated on the semiconductor layer 12. Thus, the second electrolyte layer 14 can be brought into contact and bonded with high adhesive strength and a wide contact area, which is preferable. Moreover, since the protective layer 17 mentioned later can be adhere | attached on the surface opposite to the surface laminated | stacked on the semiconductor layer 12 of the 2nd electrolyte layer 14, it is preferable.

The first electrolyte layer 13 and the second electrolyte layer 14 can move charges when the second electrolyte layer 14 contacts or approaches the first electrolyte layer 13 through the holes 18 shown in FIGS. Formed.
Further, at least a part of the periphery of the conductive layer 11 and the semiconductor layer 12 has a contact portion 15 in which the peripheral portions 13a and 14a extending outward from the periphery contact each other, and the second electrolyte layer 14 is the first electrolyte layer 14 A charge is formed so as to be movable by contact with one electrolyte layer 13.
The contact portion 15 can be provided on the entire circumference around the conductive layer 11, but may be provided on a part such as one side around the conductive layer 11, two opposite sides, and two adjacent sides.

When the second electrolyte layer 14 is formed so that charges can move between the first electrolyte layer 13, the function of the second electrolyte layer 14 for diffusing ions in the horizontal direction is effectively exhibited, The charge transfer to one electrolyte layer 13 becomes smooth. When both the first electrolyte layer 13 and the second electrolyte layer 14 are made of conductive hydrogel, they are firmly adhered to each other, and charges are efficiently transported from the semiconductor layer 12.
7 and 8 may be used in combination, but if the contact portion 15 is provided, the manufacture of the electron supplier 10 may be complicated, in that case The contact portion 15 is not provided, and only the gap between the hole 18 and the conductive fiber base material can be used as a charge transfer path.

The conductive hydrogel used for the second electrolyte layer 14 needs to cause the semiconductor layer 12 such as titanium oxide to receive an electromagnetic wave having a wavelength of at least 340 nm to 500 nm. It preferably has a transmittance. In the present specification, the term “transparent” means that the transmittance of electromagnetic waves having a wavelength of 340 nm to 500 nm is high.
The thickness of the conductive hydrogel used for the second electrolyte layer 14 is not particularly limited, but is preferably 100 μm to 1000 μm. If it is too thick, the transmittance of electromagnetic waves may decrease. If it is too thin, the charge movement speed may decrease when the ion movement distance in the horizontal direction is long.
A reinforcing material such as a woven fabric or a non-woven fabric may be placed in the conductive hydrogel as long as the electromagnetic wave transmittance is not significantly reduced.

The conductive hydrogel used for the second electrolyte layer 14 needs to cause the semiconductor layer 12 such as titanium oxide to receive an electromagnetic wave having a wavelength of at least 340 nm to 500 nm. It preferably has a transmittance. In the present specification, the term “transparent” means that the transmittance of electromagnetic waves having a wavelength of 340 nm to 500 nm is high.
The thickness of the conductive hydrogel used for the second electrolyte layer 14 is not particularly limited, but is preferably 100 μm to 1000 μm. If it is too thick, the transmittance of electromagnetic waves may decrease. If it is too thin, the charge movement speed may decrease when the ion movement distance in the horizontal direction is long.
A reinforcing material such as a woven fabric or a non-woven fabric may be placed in the conductive hydrogel as long as the electromagnetic wave transmittance is not significantly reduced.

The moisture content of the electroconductive hydrogel used for the electrolyte layers 13 and 14 can be normally set to 5 to 50 weight%, Preferably it is about 10 to 30 weight%. When the water content is low, the flexibility of the conductive hydrogel may be lowered. Moreover, ion conductivity may fall and it may be inferior to the capability to move an electric charge. If the water content of the conductive hydrogel is high, the water that exceeds the water content that can be retained by the conductive hydrogel may be detached or dried, causing the gel to shrink or the change in physical properties such as ionic conductivity to increase. Sometimes. Moreover, it may be too flexible and inferior in shape retention.
The resistivity (specific resistance) of the conductive hydrogel used for the electrolyte layers 13 and 14 is set according to the service life of the electron supply body 10 and the environment of the installation location, but is preferably 40 to 560 Ω · cm, 40 to 350 Ω · cm is more preferable.

The electroconductive hydrogel used for the electrolyte layers 13 and 14 is mainly agar, Karaya gum, gelatin, sodium alginate, polyacrylic acid or a salt thereof, polyacrylamide, polyvinyl alcohol, polystyrene sulfonic acid, polyvinyl pyrrolidone, carboxymethyl cellulose or a salt thereof. Water and an electrolyte salt are stably held in a hydrophilic resin matrix such as a hydrogel as a component or a hydrogel made of hydrophilic polyurethane or the like.
Among these hydrophilic resin matrices, in view of quality stability, adhesiveness, conductivity, shape retention, etc., a resin matrix obtained by polymerizing a polymerizable monomer such as acrylic acid or a salt thereof is preferably used. .
A hydrophilic resin matrix may be used independently and may mix and use 2 or more types as needed.

Examples of the polymerizable monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, ( (Meth) acrylic acid derivatives such as poly) glycerin (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) ) (Meth) acrylamide derivatives such as acrylamide, N, N-dimethyl (meth) acrylamide, diacetone acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, t-butylacrylamide sulfonic acid and their salts; N-vinylpyrrolidone , N-vinylform Bromide, N- vinylamide derivatives such as N- vinyl acetamide, vinyl sulfonic acid, and sulfonic acid monomers such as allyl sulfonic acid and salts thereof.
In particular, a resin matrix obtained by polymerizing a polymerizable monomer such as acrylic acid or a salt thereof is preferably used because it has a high transmittance of electromagnetic waves having a wavelength of 340 nm to 500 nm and is excellent in weather resistance.

The resin matrix of the conductive hydrogel used for the electrolyte layers 13 and 14 is subjected to a crosslinking treatment with a crosslinking agent in order to increase cohesion, or a polymerization monomer and a crosslinking monomer are polymerized to be crosslinked. It is preferable to keep them. A resin matrix in which polymer molecular chains are three-dimensionally cross-linked in this manner is preferable because it has excellent ability to retain water and a wetting agent described later.
The crosslinkable monomer is not particularly limited. For example, a polyfunctional (meth) acrylamide-based single monomer such as methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, N, N-methylene bisacrylamide, N-methylol acrylamide and the like. Multi-functional (meta) such as (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycidyl (meth) acrylate ) Acrylate monomers; tetraallyloxyethane; diallylammonium chloride and the like. Of these, polyfunctional (meth) acrylamide monomers are preferred, and N, N-methylenebisacrylamide is more preferred. In addition, the said crosslinkable monomer may be used independently and 2 or more types may be used together.

  As content of a crosslinkable monomer, 0.005-3 weight part is preferable with respect to 100 weight part of resin matrices. If the content of the crosslinkable monomer in the conductive hydrogel is small, a conductive hydrogel having excellent shape retention may not be obtained. If the content of the crosslinkable monomer is large, the number of network cross-linking points connecting the main chains will increase, and a conductive hydrogel with apparently high shape retention will be obtained, but the conductive hydrogel will become brittle and will have a tensile force. In some cases, the conductive hydrogel is likely to be cut or broken by the compression force. Further, the increase in the number of crosslinking points makes the polymer main chain hydrophobic, making it difficult to stably retain water contained in the network structure, and bleed is likely to occur.

  When a wetting agent is included in the conductive hydrogel used for the electrolyte layers 13 and 14, a decrease in the moisture content of the conductive hydrogel can be suppressed. It is preferable to adjust the wetting agent to a range of about 5 to 70% by weight, preferably about 20 to 50% by weight from the viewpoint of adhesiveness and shape retention. If the content of the wetting agent in the electroconductive hydrogel is low, the moisturizing power of the electroconductive hydrogel will be poor, the moisture will easily evaporate, and the electroconductive hydrogel will be less stable over time or less flexible. The adhesiveness may decrease. When the content of the wetting agent is large, the viscosity becomes too high during the production of the conductive hydrogel, the handleability is lowered, and air bubbles may be mixed in when forming the conductive hydrogel.

The wetting agent is not particularly limited, and for example, polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, glycerin, pentaerythritol, sorbitol; one or two or more of these polyhydric alcohols are polymerized as monomers. Examples of polyols include: sugars such as glucose, fructose, sucrose, and lactose. The wetting agent may be used alone or in combination of two or more. Moreover, you may have functional groups, such as an ester bond, an aldehyde group, and a carboxyl group, in the molecule | numerator of polyhydric alcohol, or the terminal of a molecule | numerator. Of these, polyhydric alcohols are preferred because they impart elasticity to the conductive hydrogel in addition to the action of retaining moisture. Of the polyhydric alcohols, glycerin is particularly suitable in terms of long-term water retention. Polyhydric alcohols can be used by selecting one or two or more of them. When it is necessary to increase the elasticity of the conductive hydrogel, an effect can be obtained by adding a known filler such as titanium oxide, calcium carbonate, or talc.
The conductive hydrogel used for the electrolyte layers 13 and 14 may be appropriately added with a preservative, an antifungal agent, a rust inhibitor, an antioxidant, a stabilizer, a surfactant, a colorant, and the like as necessary. good.

The electrolyte salt contained in the conductive hydrogel used for the electrolyte layers 13 and 14 can be arbitrarily selected from electrolyte salts commonly used as charge transport layers. Such a salt is not particularly limited as long as it can impart ionic conductivity to the conductive hydrogel. For example, a halogenated alkali metal salt such as sodium halide such as NaCl, potassium halide such as KCl, Halogenated alkaline earth metal salts such as magnesium halide and calcium halide; other metal halides such as LiCl; sulfates, nitrates, phosphates, chlorines of various metals such as K ₂ SO ₄ and Na ₂ SO ₄ Acid salts, perchlorates, hypochlorites, chlorites, ammonium salts, fluorine-containing electrolyte salts such as LiPF ₆ and LiBF ₄ and inorganic salts such as various complex salts; acetic acid, benzoic acid, lactic acid, tartaric acid, etc. Monovalent organic carboxylates; monovalent or divalent salts of polyvalent carboxylic acids such as phthalic acid, succinic acid, adipic acid and citric acid; Metal salts of organic acids such as phonic acid and amino acids; organic ammonium salts; salts of polymer electrolytes such as poly (meth) acrylic acid, polyvinyl sulfonic acid, poly t-butylacrylamide sulfonic acid, polyallylamine, and polyethyleneimine It is done. In addition, even when the hydrogel is insoluble or dispersed, it can be used that dissolves in the hydrogel over time, such as silicate, aluminate, metal oxide. And metal hydroxides.
The content of the electrolyte salt in the conductive hydrogel is preferably 1 to 20% by weight. If it is higher than this range, it is difficult to completely dissolve the electrolyte salt in water, and it may precipitate as crystals in the conductive hydrogel, or may inhibit dissolution of other components. If it is lower than this range, the ion conductivity may be inferior.

If the electroconductive hydrogel used for the electrolyte layers 13 and 14 contains electrolyte salt, it will become ionic conductivity and a charge movement is possible, but when a redox agent is also included, a charge movement becomes smoother. . Examples of such a redox agent include organic materials such as a quinone-hydroquinone mixture and inorganic materials such as S / S ²⁻ and I ₂ / I ⁻ . Further, LiI, NaI, KI, CsI, metal iodides or as CaI _2, tetraalkylammonium iodide, pyridinium iodide, iodine compounds such as quaternary ammonium compounds, such as imidazoline iodide also suitably used .

  Examples of the method for producing the conductive hydrogel used for the electrolyte layers 13 and 14 include dissolving or dispersing in water a solution in which a polymerizable monomer, a crosslinkable monomer, a wetting agent, a polymerization initiator, and an electrolyte salt are added. Crosslinking, polymerizing method, polymerizable monomer, crosslinkable monomer, wetting agent and polymerization initiator dissolved or dispersed in water to crosslink and polymerize electrolyte salt in polymer matrix A method of impregnation, adding a crosslinking agent to a dispersion in which an electrolyte salt is dissolved or dispersed in a linear polymer in which only a polymerizable monomer is dispersed in water and polymerized in the presence of a wetting agent. And a method of forming a resin matrix by cross-linking reaction between a glassy polymer and a cross-linking agent.

As a method of forming the electrolyte layers 13 and 14, a known method can be adopted. For example, the method of apply | coating on the conductive layer 11 or the semiconductor layer 12 by coating methods, such as gravure coating, bar coating, and screen coating, can be mentioned.
When the conductive hydrogel is used as the electrolyte layers 13 and 14, the conductive hydrogel has adhesiveness. Therefore, even if a conductive hydrogel sheet formed in advance is attached to the conductive layer 11 or the semiconductor layer 12. good. This method is preferable when the electron supply body 10 is mass-produced by a roll-to-roll because a sheet of conductive hydrogel of a roll wound body can be used as the electrolyte layers 13 and 14.
When the electrolyte layers 13 and 14 are single wafers, a conductive layer obtained by dissolving or dispersing in water a polymerized monomer, a crosslinkable monomer, a wetting agent, a polymerization initiator and an electrolyte salt is added. 11 or the semiconductor layer 12 may be applied to form a sol-like electrolyte layer, and then gelled by radical polymerization.
When the electron supply body 10 is mass-produced by roll-to-roll, when the electrolyte layers 13 and 14 are integrated and wound on a roll, or when cut and stacked on a sheet, the free surfaces (outside of the electrolyte layers 13 and 14) It is preferable to laminate release paper on the surface exposed to the surface.

≪Protective body 22≫
As the body 22 to be protected, in addition to steel containing iron such as steel (stainless steel and the like), it is possible to prevent corrosion including nickel, titanium, copper and zinc. In addition, the electron supply body 10 is adhered to a surface layer made of an ion-permeable oxide film such as rust existing directly on the surface of a bare metal that is not covered with a concrete layer or a paint film. Thus, it is possible to prevent corrosion.

When the to-be-protected body 22 is embedded in the concrete layer 21, it is said that there is water or a gel-like substance containing water in the extremely small voids in the concrete layer 21, and the ions contained therein are , OH ⁻ , Na ⁺ , Ca ²⁺ , K ^{+ and the} like are said to be the main ones. That is, the concrete layer 21 is a solid electrolyte layer having a remarkably large electric resistance, and can function as an ion conductive layer formed by these ions. And since the water | moisture content in the concrete layer 21 discharge | releases a water | moisture content to air by drying or absorbs the water | moisture content in air by rain water and the daily range of temperature, the concrete layer 21 will be in an absolutely dry state. There is no.

Moreover, the to-be-corroded body which can apply the anti-corrosion structure of this invention is applicable also to the to-be-corroded body in which the coating film of the coating was formed in the surface. The coating film looks like an insulating layer at first glance, but there are many cracks and fine holes that cause corrosion on the surface of the coating film that requires anticorrosion. These cracks and holes penetrate to the body to be protected. Since the cracks and holes cannot block moisture and air, moisture is present. Therefore, ions can move in this portion and become ionic conductive, so that the present invention can be used to prevent corrosion. And since this anticorrosion should just be performed with respect to the part of this crack and a fine hole, an extremely narrow area will be anticorrosive. Therefore, even if the amount of electrons supplied from the electron supplier 10 is small, extremely effective anticorrosion can be achieved.
In addition, when a conductive hydrogel is used as the electrolyte layers 13 and 14, a part of the conductive hydrogel penetrates into cracks and fine holes on the surface and is in contact with the object to be protected or located very close to it. Therefore, it is possible to prevent corrosion more reliably.

≪Protective layer 17≫
As shown in FIG. 6, in the electron supply body 10 of this embodiment, a protective layer 17 capable of transmitting electromagnetic waves is disposed on the second electrolyte layer 14. The protective layer 17 is preferably a flat member such as a film, sheet, or plate, and is preferably formed so as to cover at least the entire surface of the second electrolyte layer 14.
The protective layer 17 is located on the surface and blocks water and air to prevent the second electrolyte layer 14 from becoming dirty, deteriorated, or damaged. Further, since the conductive layer 11, the semiconductor layer 12, and the first electrolyte layer 13 existing further inside do not come into contact with water, their deterioration and alteration are prevented.
The protective layer 17 is preferably laminated in advance on the second electrolyte layer 14, but may be laminated when the electron supply body 10 is waterproofed.

  The material for forming the protective layer 17 is not particularly limited as long as it can transmit electromagnetic waves and has water impermeability. However, in the present invention, the semiconductor layer 12 such as titanium oxide has a wavelength region of at least 340 nm to 500 nm. Any device that can generate electrons by receiving electromagnetic waves is preferable because natural light can be used effectively. Therefore, the protective layer 17 is preferably transparent. Transparent here means that the total light transmittance of visible light having a wavelength of 340 nm to 500 nm is high, but unless it is 0, the lower limit is not particularly limited, and the object on which the electron supply body 10 is installed. It can be selected as appropriate according to the environment.

  The preferable total light transmittance of the protective layer 17 is 50% or more at a wavelength of 340 nm to 420 nm, and 70% or more at a wavelength of 340 nm to 500 nm. If the total light transmittance is high, there is no problem even if the haze (cloudiness) is high. Rather, when the electron supplier 10 is installed on the underpass of a car that passes underneath or on the underway of a highway, the surface (free surface) of the electron supplier 10 has frosted glass-like irregularities so that the headlight does not reflect at night. It is preferable from the viewpoint of preventing traffic accidents. Examples of such a transparent material include a glass plate and a plastic film. Among these, a plastic film is preferable because it is lighter than a glass plate, can be wound up in a roll shape, and has excellent impact resistance.

  The resin for forming the plastic film used as the protective layer 17 is not particularly limited as long as it can be formed into a water-impermeable film, but polytetrafluoroethylene (PTFE) or ethylene-tetrafluoroethylene copolymer. A fluorine resin such as (ETFE), an epoxy resin, or an acrylic resin film is preferable because it is excellent in antifouling properties and weather resistance. In particular, when a fluororesin is formed into a film having a thickness of 25 μm, a total light transmittance of 90% or more in an ultraviolet region to a visible light region of 300 nm to 500 nm can be obtained. Is preferable. In addition, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), tetraacetyl cellulose (TAC), polyester sulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF) , Polyetherimide (PEI), polyacetal, transparent polyimide-based polymer, polyethersulfone, and the like.

The protective layer 17 is preferably one that does not interfere with the transmission of electromagnetic waves received by the semiconductor layer 12, and an ultraviolet absorbing functional group such as a carbonyl group or an aromatic group can be formed by appropriately selecting the type of semiconductor or sensitizing dye. Either a plastic film having a plastic film or a plastic film having no UV-absorbing functional group can be used. When a film having a UV-absorbing functional group is used as the protective layer 17, the film is easily deteriorated by ultraviolet rays. It is preferable to improve the property.
Although there is no restriction | limiting in particular as thickness of the plastic film used for the protective layer 17, As long as physical strength is satisfy | filled by water impermeability, it is preferable that it is thin from transparency and cost, 50-500 micrometers, Preferably it is 50 A range of ˜200 μm is selected. Such a plastic film may be stretched to improve physical strength, or a plurality of layers of the same kind or different kinds may be laminated.

≪Other configuration examples of electron supplier≫
The electron supply body 10A shown in FIG. 2 has a configuration in which the first electrolyte layer 13 is formed on the other surface of the conductive layer 11 via the insulating layer 16 in the electron supply body 10 shown in FIG. In this electron supplier 10A, the first electrolyte layer 13 does not contact the conductive layer 11 or the semiconductor layer 12, but via the second electrolyte layer 14 connected by the contact portion 15 of the peripheral portions 13a and 14a. The charge can move between the semiconductor layer 12 and the first electrolyte layer 13. As the insulating layer 16, a plastic film, a glass sheet, or the like can be used. Note that since the insulating layer 16 does not have to be transparent, the conductivity of the conductive layer 11 can be improved by using a metal layer such as nickel or titanium.
By configuring the electron supply body 10A in this way, it can be used as a support for forming the conductive layer 11 and the semiconductor layer 12, and for example, a paste-like conductive material can be directly applied using the insulating layer 16 as a film substrate. Alternatively, since the conductive layer 11 can be formed by being embedded so as to embed the fiber base material, there is no permeation of the conductive material to the back side, and the formation of the conductive layer 11 is facilitated.

The electron supplier 10B shown in FIG. 3 has a configuration in which the electrolyte layers 13 and 14 are within the plane of the conductive layer 11 and do not have the contact portions 15 of the peripheral portions 13a and 14a in the electron supplier 10 shown in FIG. . The sizes of the electrolyte layers 13 and 14 and the conductive layer 11 may be substantially the same, but when a part of the conductive layer 11 is exposed from the electrolyte layers 13 and 14, it may be used as an electron discharge point. It is preferable because it is possible. When forming the conductive layer 11, it is preferable to form a gap between fibers and a hole 18 penetrating the conductive layer 11 in order to ensure ion permeability.
In the case where the protective layer 17 is provided, it is formed on the second electrolyte layer 14 and is preferably formed so as to cover the entire surface of the second electrolyte layer 14 and the semiconductor layer 12.

The electron supply body 10C shown in FIG. 4 has a configuration in which the second electrolyte layer 14 is not formed in the electron supply body 10B shown in FIG.
In addition, since the second electrolyte layer 14 does not exist, the first electrolyte layer 13 plays a role of directly receiving the positive charges of the semiconductor from which electrons have been emitted. Therefore, in this case, it is necessary to form a gap between fibers or a through hole 18 in the conductive layer 11 in order to transmit ions.
In the case where the protective layer 17 is provided, it is preferably formed so as to cover the entire surface of the semiconductor layer 12 using an adhesive or the like.

Hereinafter, the present invention will be specifically described with reference to examples.
The electron supply body 10 shown in FIGS. 1-3 is produced as Examples 1-3 of the electron supply body in the following manner, and the electron supply body shown in FIGS. 4, 10, and 11 is used as Comparative Examples 1-3 of the electron supply body. 10 was produced. And the anti-corrosion structure 20 shown in FIG. 6 as an anti-corrosion structure using Examples 4-7 of the electron supply body of this invention was produced, and the IV characteristic of the electron supply body 10 was measured.

<< Example 1 of an electron supplier >>
The test body of the electron supply body 10 of FIG. 1 was created in the following manner.
<Conductive layer 11>
After applying and drying a conductive carbon paste in which graphite is dispersed from the surface of a glass nonwoven fabric having a basis weight of 30 g / m ² , the carbon paste is also applied and dried from the back side, the width is about 30 mm, the length is A 50 mm conductive layer 11 was prepared. The adhesion amount of the carbon paste was about 60 g / m ² by dry weight. The thickness of the conductive layer 11 cannot be measured accurately because the surface is not smooth, but is approximately 100 μm to 110 μm.
<Semiconductor layer 12>
Titanium oxide paste (C-Paste manufactured by Showa Denko) in which anatase-type titanium oxide is dispersed in a width of 30 mm so that the conductive layer 11 is exposed as a 10 mm strip on both upper and lower ends in the length direction on one side of the conductive layer 11 ) Was applied and dried to form a semiconductor layer 12 made of TiO ₂ having a thickness of about 10 μm (dry weight: 15 g / m ² ).

<Electrolyte layers 13 and 14>
An adhesive conductive hydrogel sheet having a thickness of about 0.6 mm, a width of about 60 mm, and a length of about 30 mm on both surfaces of the conductive layer 11 and the semiconductor layer 12 and imparted with ionic conductivity (Sekisui The first electrolyte layer 13 and the second electrolyte layer 14 made of “Technogel CR-S” manufactured by Kasei Kogyo Kogyo Co., Ltd. were overlapped and adhered in the center in the width direction.
<Contact part 15>
Example 1 of the electron supply body 10 of FIG. 1 by bringing the peripheral portions 13a, 14a having a width of 15 mm on both sides of the first electrolyte layer 13 and the second electrolyte layer 14 where the conductive layer 11 does not exist into close contact to form the contact portion 15. It was created.
<Others>
A copper tape having a width of 10 mm was applied to the exposed portion of the conductive layer 11 with a length of 10 mm with a conductive adhesive over the entire width in the longitudinal direction to provide an installation point for the electron drainage point.
In this test body, the hole 18 was not provided in the conductive layer 11 in order to facilitate examination of the test result.

The hydrogel layer of a commercially available biomedical electrode pad obtained by laminating a hydrogel layer containing a silver layer, a silver chloride layer and an electrolyte salt on a synthetic resin sheet and extending a part of the silver chloride layer as an electrode is a first electrolyte layer. The silver-silver chloride electrode of the electrode pad as one electrode and the copper tape affixed to the conductive layer 11 as the other electrode is 40 mW / cm ² with a reflex lamp for photography indoors. The semiconductor layer 12 was irradiated with light.
An electronic load device was connected between the two electrodes, and the current-voltage characteristics (IV characteristics) were measured by changing the load resistance to obtain an IV curve shown in “first embodiment” of FIG. .

<< Example 2 of an electron supplier >>
Except that an insulating layer 16 made of a square PET film having a side length of about 35 mm is sandwiched between the conductive layer 11 and the first electrolyte layer 13 so as to cover the entire surface of the conductive layer 11. 2 was prepared as Example 2 in the same manner as in Example 1 of the supply body.
In the same manner as in Example 1 of the electron supplier, an IV curve shown in “Second Example” in FIG. 9 was obtained. In Example 2, since an electric current was obtained even if the ion permeability of the conductive layer 11 was completely inhibited, the second electrolyte layer 14 in contact with the first electrolyte layer 13 was contacted by the contact portion 15. It was confirmed that charges were transferred from the semiconductor layer 12.
However, since the short-circuit current density (current density at a voltage of 0 volt) is reduced to less than half compared to Example 1 of the electron supply body, ion permeation provided by the gaps in the fiber base material of the conductive layer 11 It can be seen that there is a certain effect on the charge transfer.

<< Example 3 of an electron supplier >>
Example 3 is shown in Example 3 in the same manner as Example 1 of the electron supplier except that the conductive gel sheet is a square having a side length of about 28 mm and the contact part 15 of the electrolyte layers 13 and 14 is not provided. The electron supplier 10B was prepared.
In the same manner as in Example 1 of the electron supplier, the IV special curve shown in “Third embodiment” of FIG. 9 was obtained. In Example 3, since an electric current was obtained without providing the contact portion 15, the charge from the semiconductor layer 12 was passed through the first electrolyte layer 13 due to the ion permeability of the conductive layer 11 through the gap between the fibers. It was confirmed that it moved.
However, since the short-circuit current density is greatly reduced as compared with the electron supply examples 1 and 2, the present example in which neither the holes 18 nor the contact portions 15 of the electrolyte layers 13 and 14 are provided in the conductive layer 11. In FIG. 5, it can be seen that the contact portion 15 is more effective in transferring the charge than the ion permeability imparted by the gap between the fiber base materials of the conductive layer 11.

≪Comparative example 1 of electron supply body≫
An electron supply body 10C of FIG. 4 was produced as Comparative Example 1 in the same manner as in Example 3 of the electron supply body except that the second electrolyte layer 14 was not provided.
In the same manner as in Example 1 of the electron supplier, an IV curve shown in “fourth embodiment” of FIG. 9 was obtained. In Comparative Example 1, since the current flowed without providing the second electrolyte layer 14, the ion permeability of the conductive layer 11 due to the gap between the fibers causes the semiconductor layer 12 to pass through the first electrolyte layer 13. It was confirmed that the charge moved.
And since compared with Example 1 of an electron supply body, since the short circuit current density has fallen significantly similarly to Example 3, in the comparative example 1 which does not provide the 2nd electrolyte layer 14, it is 2nd. It can be seen that the electrolyte layer 14 has a certain effect on the movement of charges. However, since the short-circuit current density is slightly reduced as compared with Example 3 of the electron supply body provided with the second electrolyte layer 14, when the ion permeability of the conductive layer 11 is not sufficient, It turns out that the effect of the 2nd electrolyte layer 14 may not fully be exhibited.

<< Comparative Example 2 of Electron Supplier >>
Comparative Example 2 is the same as Comparative Example 1 of the electron supplier except that the insulating layer 16 is formed between the conductive layer 11 and the first electrolyte layer 13 in the same manner as in Example 2 of the electron supplier. As shown in FIG.
In the same manner as in Example 1 of the electron supplier, an attempt was made to measure the IV characteristics, but both the short-circuit current density and the open-circuit voltage (voltage at a current of 0 mA / cm ² ) were 0, and the IV curve was It was not obtained. In Comparative Example 2, it was found that the ion permeability of the conductive layer 11 was completely inhibited and the contact portion 15 was not provided, so that no charge was transferred from the semiconductor layer 12 and no current flowed.

≪Comparative example 3 of electron supply body≫
11 was produced as Comparative Example 3 in the same manner as in Comparative Example 2 of the electron supply except that the second electrolyte layer 14 was formed in the same manner as in Example 3 of the electron supply.
In the same manner as in Example 1 of the electron supplier, an attempt was made to measure the IV characteristics, but both the short-circuit current density and the open-circuit voltage were 0, and no IV curve was obtained. In Comparative Example 3, the ion permeability of the conductive layer 11 is completely blocked, and the contact portion 15 is not provided. Therefore, even if the second electrolyte layer 14 is provided, the charge from the semiconductor layer 12 is reduced. It was found that there was no movement and no current flowed.

<< Anti-corrosion structure using Examples 4 to 7 of the electron supplier >>
Example 4-7 of an electron supply body are produced in the following manner, and using these, the anticorrosion structure shown by the code | symbol 20 in FIG. 12 according to FIG. It was measured.
Basis weight that PET nonwoven fabric and a basis weight of 25 g / ^{m 2} were used two kinds of nonwoven glass nonwoven 30 g / ^{m 2,} and the width of the conductive layer 11 and 100 mm, except that the approximately 120mm of length In the same manner as in Example 1 of the electron supply body, two conductive layers 11 using two kinds of fiber base materials are formed, and a total of four 100 mm square semiconductor layers 12 made of TiO ₂ are formed on one side. A conductive layer / semiconductor layer laminate was prepared.
A plurality of circular holes 18 having a diameter of 3 mm were provided in the obtained four conductive layer / semiconductor layer stacks so as to be obliquely aligned with the sides of the conductive layer 11 in the pattern of FIG. The intervals between the holes 18 were arranged so that the distance between the centers of the holes arranged obliquely on the side was 12 mm. The hole 18 penetrates both the conductive layer 11 and the semiconductor layer 12 as shown in FIG.
Conductive layer / semiconductor layer laminate using the first electrolyte layer 13 and the second electrolyte layer 14 made of a conductive hydrogel having a width of 120 mm and a length of about 100 mm in the same manner as in Example 1 of the electron supplier. The contact portions 15 having a width of 10 mm were provided on both sides of the laminate, and four Examples 4 to 7 of the electron supply body of FIG. 1 using two types of fiber base materials were produced.

A protective layer 17 made of acrylic / fluorine or ETFE is laminated on the four examples 4 to 7 of the obtained electron supply body so as to cover the entire surface of the semiconductor layer 12 on the second electrolyte layer 14. And the Examples 4-7 of the following four types of electron supply bodies with a protective layer were produced.
No. 1: The fiber base material of the conductive layer 11 is PET nonwoven fabric, and the protective layer 17 is acrylic / fluorine.
No. 2: The fiber base material of the conductive layer 11 is PET nonwoven fabric, and the protective layer 17 is ETFE.
No. 3: The fiber base material of the conductive layer 11 is a glass nonwoven fabric, and the protective layer 17 is acrylic / fluorine.
No. 4: The fiber base material of the conductive layer 11 is a glass nonwoven fabric, and the protective layer 17 is ETFE.
Here, “acrylic / fluorine” of the weather-resistant film is “acrylic resin film containing UV absorber co-extruded with fluororesin (manufactured by Mitsubishi Rayon, trade name: acrylene) 50 μm”, and “ETFE” “Ethylene tetrafluoroethylene copolymer film (Asahi Glass Co., Ltd., trade name: Aflex) 25 μm”.

Using rebars (25 cm in length, φ6 mm) as the body to be protected 22, the rebars are arranged in a grid pattern at regular intervals of 6 bars in each direction so as to be a central layer of a concrete layer with a thickness of 6 cm and a 30 cm side. A lead wire for supplying electrons to the reinforcing bar and a lead wire (not shown) for measuring the potential of the reinforcing bar were drawn out and embedded in the mortar. The surface layer 21 made of a concrete layer was formed by subjecting the surface of the concrete substrate with reinforcing bars to kelen (base adjustment) using a diamond cup.
The specification of the mortar was set to cement 1, standard sand 3, and water 0.5 by mass ratio by blending the mortar described in JIS R 5201 “Cement physical test method”. In this case, the water cement ratio is 0.50. The cement used was ordinary Portland cement.
The four types of obtained electron supply bodies with protective layers of the conductive layers 11 of Examples 4 to 7, the 10 cm square side where the semiconductor layer 12 and the electrolyte layers 13, 14 are overlapped with the side of the concrete layer 21. In this manner, the first electrolyte layer 13 was used to adhere to the center of the base material adjustment surface of the concrete layer 21. Electron draining points were provided on the copper tape of the conductive layer 11, and the conductive wires 23 were attached with solder. And the lead wire 23 is connected to the lead wire for electron supply drawn out from the to-be-corroded body 22, and the anticorrosion structure shown by the code | symbol 20 in FIG. 12 is comprised, The anticorrosion structure using Examples 4-7 of an electron supplier did.

≪Measurement of potential and current density≫
In order to prevent drying and swelling from the end surfaces of the first and second electrolyte layers 13 and 14 when the anticorrosion structure using Examples 4 to 7 of the electron supply body is installed outdoors, an acrylic / fluorine weathering film is used. The ribbon was cut into a ribbon shape and covered with four sides of the protective layer 17 using an epoxy resin adhesive, and waterproofed.
In order to confirm the movement of electrons to the to-be-protected body 22 at the time of light reception of the electron supply body 10, a non-resistance ammeter (Toho Giken Co., Ltd.) is placed between the lead wires 23 of the anticorrosion structure using Examples 4-7 of the electron supply body AM-02) 24 was provided. Further, in order to measure the electric potential of the reinforcing bar 22, a manganese dioxide electrode was embedded as a reference electrode 25 on the back surface (surface not to be clean) of the concrete layer 21 and fixed with mortar, and connected to an electrometer 26 using a lead 27. And the anti-corrosion structure using Examples 4-7 of the electron supply body to which the electrometer 26 was connected using the conducting wire 28 to the reinforcing bar electric potential measurement conducting wire attached to the reinforcing bar 22, and the measuring apparatus shown in FIG. 12 was connected. Specimens were used. Note that copper wires coated with resin were used as the conductive wires 23, 27, and 28 for electrical connection.
The non-resistance ammeter 24 is connected so as to show a positive current value when the current flows in the direction of the electron supply body 10 → the conductive wire 23 → the reinforcing bar 22 as shown in FIG. When moving in the direction of the conductive wire 23 → the reinforcing bar 22, the current flowing in the direction of the reinforcing bar 22 → the conductive wire 23 → the electron supplier 10 is observed, and thus a negative current value is indicated.

In order to measure the potential of the corrosion-protected body 22 having the anticorrosion structure using Examples 4 to 7 of the electron supply body, the electron supply body 10 was turned upside down so as not to be exposed to direct sunlight outdoors. The center of the four sides was supported by four 10 cm cubic mounting tables. Using a small data logger, the potential of the reinforcing bar 22 was measured at a frequency of once per hour, and data was collected. The rebar potential test results are shown in FIGS. 13 to 16 and the generated current density test results are shown in FIGS. The generated current density is 0.1 mA / m ² (1 μA) since the cross-sectional area of the concrete layer 21 is 100 cm ² if the current generation amount measured by the resistanceless ammeter 24 is 1 μA. / 100 cm ² ).
The lower peak corresponds to daytime, and the upper peak corresponds to nighttime. The experiment started from 19:30, but this is shown as the starting point of the day for convenience. If midnight is the starting point of the day, the peak will be shifted to the left by four and a half hours.
In the anticorrosion structure using Examples 4 to 7 of the electron supplier, electrons are supplied to the reinforcing bars 22 from Examples 4 to 7 of the electron supplier and are transported by the ionic conductivity of the electrolyte layers 13 and 14. It was confirmed that when the electric charge is reduced by the electrons of the reinforcing bar 22, a current flows and the potential of the reinforcing bar is lower than its natural potential. However, the anticorrosion structure using Example 3 of the electron supplier was somewhat dull, although a decrease in rebar potential and generation of current were observed. This phenomenon is presumed to be caused by some abnormality in the sample preparation process.

Since the potential of the reinforcing bar of the anticorrosion structure using Examples 1, 2 and 4 of the electron supply body is lowered to −100 mV or less of the reinforcing bar natural potential, which is normally considered to be an electric corrosion-proof potential, the electron supply of the present invention is performed. It can be seen that the body has sufficient capacity for cathodic protection.
17 to 20, it was found that if a current density of 3 mA / m ² (30 μA / 100 cm ² ) or more is obtained, the rebar potential can be lowered to −100 mV or less of the natural potential. Although the reason is not clear, the anticorrosion rebars using the electron supplier examples 1, 2 and 4 suddenly drop in potential when exposed to light at dawn, and the generated current density is low at night. When the supply of electrons stops at 0, it rises sharply halfway. The rise then calms down and does not return to the rebar natural potential. Moreover, the generated current density does not show a positive value from FIGS. Therefore, it turns out that a corrosion current does not flow into the reinforcing bar at night.
Further, according to FIGS. 14 and 16, in Examples 2 and 4 of the anticorrosion structure using ETFE as the protective layer, the time during which the daytime rebar potential decreases to −100 mV or less of the natural potential is 1 day. Therefore, it is understood that the anticorrosion effect is excellent and preferable. This is probably because the acrylic / fluorine weather-resistant film has ultraviolet absorption, and ETFE has no ultraviolet absorption.

As described above, the case where the electron supply body of the present invention is used as a working electrode for cathodic protection has been described. However, dye sensitization is performed by directly laminating an electrode activated with platinum or carbon as a counter electrode on the first electrolyte layer. It can also be used as a working electrode of a solar cell.
Actually, Example 5 (No. 2: Conductive layer 11) of an electron supply body with a protective layer used for measurement of the potential and current density of the object to be protected by the anticorrosion structure using Examples 4 to 7 of the electron supply body. The same fiber base material as PET nonwoven fabric and protective layer 17 as ETFE) was prepared, and the first electrolyte of the sample was prepared using the large biological electrode pad used in Example 1 of the electron supply body. A hydrogel layer of an electrode pad was attached to the entire surface of the layer 13, and a solar cell was produced using the silver-silver chloride electrode of the electrode pad as one electrode and the copper tape attached to the conductive layer 11 as the other electrode. .
A closed circuit is formed in this solar cell via a non-resistance ammeter (AM-02 manufactured by Toho Giken Co., Ltd.), and 2600 Lx visible light (integrated value in the wavelength range of 300 to 400 nm is 0.027 mW) by a solar simulator indoors. / Cm ² ) was irradiated onto the semiconductor layer 12, and a current of 526 μA could be confirmed.
In the case of a high-performance dye-sensitized solar cell, it is preferable to sensitize the semiconductor layer or use a conductive layer in which a conductive material mainly composed of carbon is applied to a metal foil or a metal fiber substrate. .

  Moreover, it can also be used as a working electrode of an optical sensor or the like by directly laminating an electrode activated by platinum or carbon as a counter electrode on the first electrolyte layer. In this case as well, since a high photoelectric conversion rate is required for the electron supply body, the semiconductor layer is sensitized or a conductive layer in which a conductive material mainly composed of carbon is applied to a metal foil or a metal fiber base is used. It is preferable.

As mentioned above, although this invention has been demonstrated based on suitable embodiment, this invention is not limited to the above-mentioned example, Various modifications are possible in the range which does not deviate from the summary of this invention.
For example, when the electrolyte layers 13 and 14 are disposed on both surfaces of the conductive layer 11 and the semiconductor layer 12, one conductive hydrogel sheet is folded in half, and one side of the folded portion is used as the first electrolyte layer 13, and the other side. Can also be used as the second electrolyte layer 14. In this case, the folded portion becomes the contact portion 15 between the electrolyte layers 13 and 14. Moreover, when providing the contact part 15, you may be folded so that one of the peripheral parts 13a and 14a may extend outside from the circumference | surroundings, and may cover the other peripheral part.

DESCRIPTION OF SYMBOLS 10, 10A, 10B, 10C ... Electron supply body, 11 ... Conductive layer, 12 ... Semiconductor layer, 13 ... 1st electrolyte layer, 13a ... Peripheral part, 14 ... 2nd electrolyte layer, 14a ... Peripheral part, 15 ... Contact part, 16 ... insulating layer, 17 ... protective layer, 18 ... hole, 20 ... anticorrosion structure, 21 ... concrete layer (concrete board), 22 ... anticorrosive body (rebar), 23 ... circuit wiring.

Claims (9)

  A solidified sheet-like first electrolyte layer, a conductive layer made of a conductive base material coated and / or impregnated with a conductive material mainly composed of carbon on a base material, and a semiconductor layer that generates electrons by electromagnetic waves And a solidified sheet-like second electrolyte layer capable of transmitting electromagnetic waves in this order, and the second electrolyte layer is charged by contact or proximity with the first electrolyte layer. An electron supply body formed to be movable.   The conductive layer is a fiber base material made of a woven fabric or a non-woven fabric, and the second electrolyte layer is capable of charge transfer with the first electrolyte layer by ion permeability of a gap between the fibers. The electron supplier as described.   3. The electron supply body according to claim 1, wherein a plurality of holes through which ions can permeate are formed in the conductive layer, and charge transfer is enabled between the first electrolyte layer and the second electrolyte layer.   4. The conductive hydrogel according to claim 1, wherein both the first and second electrolyte layers are conductive hydrogels in which an electrolyte salt is contained in a water-containing gel holding at least water in a hydrophilic resin matrix. Electron supplier.   At least a part of the peripheral portions of the first electrolyte layer and the second electrolyte layer is extended from the periphery of the conductive layer and the semiconductor layer, and the peripheral portions are in contact with each other, and between the electrolyte layers. The electron supply body according to claim 1, wherein charge transfer is possible.   Furthermore, the electron supply body in any one of Claim 1 thru | or 5 with which the protective layer which can permeate | transmit electromagnetic waves is arrange | positioned on the said semiconductor layer or the 2nd electrolyte layer.   The electron supply body according to any one of claims 1 to 6, wherein the protective layer or both the protective layer and the second electrolyte layer are capable of transmitting electromagnetic waves having a wavelength of at least 340 nm to 500 nm.   The electron supplier according to any one of claims 1 to 7, wherein the semiconductor layer is a layer containing one or more metal oxides selected from titanium oxide, zinc oxide, and tin oxide.   The electron supply body according to any one of claims 1 to 8, wherein the electron supply body is used for an anticorrosion structure, a dye-sensitized solar cell, or an optical sensor.

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