Concrete Devices and Electronic Equipment

Abstract

To provide a concrete device or the like capable of improving device characteristics.SOLUTION: A concrete device 1 includes a concrete layer 10 containing concrete as an electrolyte and having a pair of end faces facing each other, an electrode 111 arranged on one of the pair of end faces of the concrete layer 10, and an electrode 112 arranged on one or the other of the pair of end faces of the concrete layer 10. The electrode 112 is a cathode containing an oxygen reduction catalyst.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a concrete device having a concrete layer and an electronic device including such a concrete device. [Background technology]

[0002] As a concrete device having a concrete layer, a concrete battery has been proposed, as disclosed in, for example, Non-Patent Documents 1 and 2. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Cement & Concrete Composites 32 (2010)829-839 [Non-patent document 2] Materials Science and Engineering 96 (2015) 012073 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in such concrete devices, there is generally a demand for improving the device characteristics, and it is desirable to provide a concrete device that can improve the device characteristics, and an electronic device that includes such a concrete device. [Means for solving the problem]

[0005] A concrete device according to one embodiment of the present disclosure includes a concrete layer containing concrete as an electrolyte and having a pair of opposing end faces, a first electrode disposed on one of the pair of end faces of the concrete layer, and a second electrode disposed on one or the other of the pair of end faces of the concrete layer. The second electrode is an air electrode containing an oxygen reduction catalyst.

[0006] An electronic device according to an embodiment of the present disclosure includes one or more concrete devices according to the above-described embodiment of the present disclosure.

[0007] In a concrete device according to one embodiment of the present disclosure, the oxygen reduction catalyst may include a metal complex or an adduct thereof and a conductive material represented by the following formula (1) or (2):

[0008] [ka] (In the formula, M is an iron atom, a manganese atom, a nickel atom, a copper atom, a zinc atom, or a cobalt atom; D 1 From D 28 are each independently a nitrogen atom, a sulfur atom, or a carbon atom, D 1 From D 28 is a carbon atom, each of the carbon atoms may independently be bonded to a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group. However, in the above formula (1), D 1 From D 16 If there are 8 or fewer carbon atoms in At least one of the carbon atoms has a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group bonded to it; or The metal complex of the formula (1) forms an adduct.

[0009] In the concrete device according to one embodiment of the present disclosure, the above-mentioned D 1 From D 16 may be a nitrogen atom or a carbon atom.

[0010] In the concrete device according to one embodiment of the present disclosure, the above-mentioned D 17 From D 28 may be a sulfur atom or a carbon atom.

[0011] In a concrete device according to one embodiment of the present disclosure, the following formula may be used:

[0012] [ka] [ka] [ka] [ka] [ka]

[0013] In a concrete device according to one embodiment of the present disclosure, the metal complex may be contained in an amount of 75% by mass or less, relative to 100% by mass, which is the total amount of the metal complex or its adduct and the conductive material.

[0014] In a concrete device according to one embodiment of the present disclosure, the conductive material may contain a carboxyl group.

[0015] In a concrete device according to one embodiment of the present disclosure, the carboxyl groups may be contained in an amount of 20 mass % or less relative to 100 mass % of the conductive material.

[0016] In the concrete device according to one embodiment of the present disclosure, the oxygen reduction catalyst may include manganese dioxide, platinum, or a carbon alloy.

[0017] In a concrete device according to one embodiment of the present disclosure, one or more gel layers composed of a hydrogel layer or an ionic gel layer may be further provided between the concrete layer and the first electrode, and between the concrete layer and the second electrode, respectively.

[0018] The concrete in the concrete layer may be, for example, ready-mixed concrete or solidified concrete. Examples of concrete devices according to an embodiment of the present disclosure include the following: A concrete battery in which the first electrode functions as a negative electrode and the second electrode functions as a positive electrode. A concentration sensor (a salt concentration sensor or a water concentration sensor) that detects the salt concentration or water concentration in the concrete layer may also be used. [Effects of the Invention]

[0019] According to one embodiment of the concrete device and electronic device of the present disclosure, the concrete layer and the first and second electrodes are respectively provided, and the second electrode is an air electrode containing an oxygen reduction catalyst, thereby making it possible to improve the characteristics of the device. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a schematic cross-sectional view showing an example of the configuration of a concrete device according to one embodiment of the present disclosure. [Figure 2]2 is a schematic cross-sectional view showing an example of the detailed configuration of the positive electrode (air electrode) shown in FIG. 1. FIG. [Figure 3] 2 is a schematic cross-sectional view showing an example of operation of the concrete device shown in FIG. 1. FIG. [Figure 4] FIG. 2 is a schematic cross-sectional view showing an example of the configuration of a concrete device according to Modification 1. [Figure 5] FIG. 10 is a schematic cross-sectional view showing an example of the configuration of a concrete device according to Modification 2. [Figure 6] FIG. 10 is a block diagram illustrating a configuration example of an electronic device according to an application example of a concrete device. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. The description will be made in the following order. 1. Embodiment (Configuration example in which a gel layer is provided between the concrete layer and the electrode) 2. Variations Modification 1 (Example of no gel layer provided) Modification 2 (Example of placing two electrodes on one end face of the concrete layer) 3. Application example (application of concrete devices to electronic devices) 4. Other Modifications

[0022] <1. Embodiment> [Configuration of concrete device] 1 is a schematic diagram showing an example cross-sectional configuration (ZX cross-sectional configuration example) of a concrete device (concrete device 1) according to one embodiment of the present disclosure. As shown in FIG. 1, the concrete device 1 of this embodiment includes a concrete layer 10, a pair of electrodes 111, 112, and one or more gel layers (in the example of FIG. 1, a pair of gel layers 121, 122).

[0023] This concrete device 1 is configured to function as, for example, the following devices. That is, for example, it functions as a battery (concrete battery) in which the electrode 111 functions as a negative electrode and the electrode 112 functions as a positive electrode. Alternatively, it is configured to function as, for example, a concentration sensor (salt concentration sensor or water concentration sensor) that detects the salt concentration (salt concentration) or water concentration in the concrete layer 10.

[0024] (Concrete layer 10) The concrete layer 10 contains concrete (fresh concrete or solidified concrete) as an electrolyte and has a pair of opposing end faces (front and back faces). That is, in the concrete layer 10, the various elements that make up the concrete are ionized into cations and anions.

[0025] Specifically, for example, in the concrete layer 10, calcium ions (Ca 2+ ), hydrogen ions (H + ) and oxygen ions (O 2- ) are each contained in an ionized state.

[0026] (electrodes 111,112) Electrode 111 is disposed on one end surface of concrete layer 10, and electrode 112 is disposed on the other end surface of concrete layer 10. In this example, as shown in FIG. 1, these electrodes 111 and 112 are attached to gel layers 121 and 122, respectively, which will be described later. When concrete device 1 functions as the concrete battery described above, electrode 111 functions as a negative electrode, and electrode 112 functions as a positive electrode.

[0027] These electrodes 111 and 112 are each composed of a combination of elements with different work functions. Specifically, in the example shown in FIG. 1, electrode 111 is composed of zinc (Zn), and electrode 112 is composed of an air electrode, which will be described later. Note that, in addition to zinc, electrode 111 may also be composed of, for example, aluminum (Al), magnesium (Mg), iron (Fe), calcium (Ca), or an alloy containing any of these metals. In this way, electrode 111 is composed using an element with a larger work function than electrode 112 (a catalyst contained in the air electrode, which will be described later).

[0028] Here, electrode 111 corresponds to a specific example of a "first electrode" and a "negative electrode" in the present disclosure, and electrode 112 corresponds to a specific example of a "second electrode" and a "positive electrode" in the present disclosure. A detailed configuration example of electrode 112 will be described later (FIG. 2).

[0029] (Gel layers 121, 122) Gel layer 121 is disposed between one end face of concrete layer 10 and electrode 111, and gel layer 122 is disposed between the other end face of concrete layer 10 and electrode 112 (see FIG. 1). In the example shown in FIG. 1, these gel layers 121 and 122 are respectively attached to a pair of end faces of concrete layer 10. Note that each of these gel layers 121 and 122 is composed of, for example, a hydrogel layer (a gel formed by adding a high molecular weight polymer to physiological saline) or an ion gel layer (a gel formed by adding a high molecular weight polymer to an ionic liquid), as shown in parentheses in FIG. 1.

[0030] Here, these gel layers 121, 122 each have the function of improving ion conduction efficiency between (at the interface) the concrete layer 10 and the electrodes 111, 112. Furthermore, it is desirable that at least one of these gel layers 121, 122 (at least one of one or more gel layers) contains one or more types of ions. As will be described in detail later, this is because the ion conductivity is improved between (at the interface) the concrete layer 10 and the electrodes 111, 112. In the example shown in FIG. 1, the gel layers 121, 122 each contain sodium ions (Na + ) and chloride ions (Cl - ) contains two types of ions.

[0031] [Detailed configuration example of electrode 112] Next, a detailed configuration example of the electrode 112 will be described with reference to FIG. 2 in addition to FIG.

[0032] First, electrode 112 of this embodiment is an air electrode (an electrode using gaseous oxygen as an electrode active material, also called an oxygen electrode) that includes an oxygen reduction catalyst described below. Specifically, as shown in Fig. 2, this electrode 112 is an air electrode with a three-layer structure that includes catalyst layer 112a supporting such an oxygen reduction catalyst, current collector layer 112b, and water-repellent layer 112c.

[0033] The catalyst layer 112a contains, for example, a carbon material (carbon black, activated carbon, graphite, etc.), a binder, and an oxygen reduction catalyst. The thickness of this catalyst layer 112a is not particularly limited, but can be, for example, 0.01 to 100 μm. When the thickness is equal to or greater than the lower limit, the electrode has excellent durability. When the thickness is equal to or less than the upper limit, the electrode performance is less likely to deteriorate. In addition, the oxygen reduction catalyst may, for example, be one containing a metal complex or an adduct thereof and a conductive material, as described below, or one containing manganese dioxide (MnO), platinum (Pt), or a carbon alloy. Of these, it can be said that the oxygen reduction catalyst containing a metal complex or an adduct thereof and a conductive material, as described below, is desirable.

[0034] As the current collector layer 112b, for example, SUS (Steel Use Stainless), nickel (Ni) mesh, carbon paper, etc. are used.

[0035] For example, a PTFE (polytetrafluoroethylene) porous film or a polymethylpentene silicone resin, which has water repellency and high gas permeability, is used as the water repellent layer 112c.

[0036] (Examples of metal complexes or their adducts) Here, the above-mentioned metal complex or adduct thereof is represented, for example, by the following formula (1) or (2): The metal complex or adduct thereof may be used alone, or two or more types of metal complexes or adducts thereof may be used in combination.

[0037] [ka] (In the formula, M is an iron atom, a manganese atom, a nickel atom, a copper atom, a zinc atom, or a cobalt atom; D 1 From D 28 are each independently a nitrogen atom, a sulfur atom, or a carbon atom, D 1 From D 28 is a carbon atom, each of the carbon atoms may independently be bonded to a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group. However, in the above formula (1), D 1 From D 16 If there are 8 or fewer carbon atoms in At least one of the carbon atoms has a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group bonded to it; or The metal complex of the formula (1) forms an adduct.

[0038] The bond between a nitrogen atom and M means that the nitrogen atom is coordinated to M. A halogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 8 carbon atoms may further be bonded to M as a ligand. An anionic counter ion may also be present to make M electrically neutral. Furthermore, M may exist as an adduct to which an electrically neutral molecule is added.

[0039] The valence of M is not particularly limited. A halogen atom, a hydroxyl group, or an (alkyloxy)alkoxy group having 1 to 8 carbon atoms may be bonded as a ligand (for example, an axial ligand) so that the metal complex or its adduct is electrically neutral, and an anionic counter ion may be present. Examples of anionic counter ions include halide ions, hydroxide ions, nitrate ions, and sulfate ions. The alkyl group in the (alkyloxy)alkoxy group having 1 to 8 carbon atoms may have a linear, branched, or cyclic structure.

[0040] Here, halogen atoms include fluorine, chlorine, bromine, and iodine.

[0041] The alkyl group refers to a linear or branched monovalent hydrocarbon group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, and an n-hexyl group.

[0042] Here, the cycloalkyl group represents a cyclic monovalent hydrocarbon group. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, and a 2,2-dimethylcyclopropyl group.

[0043] The alkenyl group refers to a linear or branched monovalent hydrocarbon group containing a double bond. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl.

[0044] Here, the alkynyl group refers to a linear or branched monovalent hydrocarbon group containing a triple bond. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a (1-butynyl group) 1-butyn-1-yl group, a (2-butynyl group) 2-butyn-1-yl group, a (3-butynyl group) 3-butyn-1-yl group, a (1-methyl-2-propynyl group) 1-methyl-2-propyn-1-yl group, a (2-methyl-3-butynyl group) 2-methyl-3-butyn-2yl group, a (1-pentynyl group) 1-pentyn-1-yl group, a (2-pentynyl group) Examples include (1-pentynyl) 2-pentyn-1-yl, (3-pentynyl) 3-pentyn-2-yl, (4-pentynyl) 4-pentyn-1-yl, 1-methyl-2-butynyl (1-methyl-2-butyn-1-yl), (2-methyl-3-pentynyl) 2-methyl-3-pentyn-1-yl, (1-hexynyl) 1-hexyn-1-yl, and (1,1-dimethyl-2-butynyl) 1,1-dimethyl-2-butyn-1-yl.

[0045] The aryl group refers to a monovalent aromatic hydrocarbon group. The number of carbon atoms in the aryl group is preferably 6 to 40, and more preferably 6 to 30. Examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthryl group, an anthracenyl group, a benzophenanthryl group, a benzanthracenyl group, a chrysenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthracenyl group, a perylenyl group, and a helicenyl group.

[0046] The alkylsulfonyl group refers to a monovalent group in which an alkyl group is bonded to a sulfonyl group. The alkyl group in the alkylsulfonyl group can be any of the groups described above as the "alkyl group." The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, n-pentylsulfonyl, isopentylsulfonyl, tert-pentylsulfonyl, neopentylsulfonyl, 2,3-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1-methylbutylsulfonyl, n-hexylsulfonyl, isohexylsulfonyl, and 1,1,2-trimethylpropylsulfonyl.

[0047] The alkoxy group refers to a monovalent group to which a hydrocarbon group is bonded via an ether bond. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and an isohexyloxy group.

[0048] The alkylthio group refers to a group in which the oxygen atom in the ether bond of an alkoxy group is substituted with a sulfur atom. The number of carbon atoms in the alkylthio group is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, an n-pentylthio group, an n-hexylthio group, and an isopropylthio group.

[0049] The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkylsulfonyl group, alkoxy group, and alkylthio group may be unsubstituted, or may be substituted with one or more substituents such as halogen, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkylthio group, cyano group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and sulfo group.

[0050] D 1 From D 16 is preferably a nitrogen atom or a carbon atom, and D 17 From D 28 is preferably a sulfur atom or a carbon atom. 1 From D 16 The number of nitrogen atoms in the group is preferably 2 to 12, and more preferably 4 to 8. 17 From D 28 The number of sulfur atoms is preferably 2 to 10, and more preferably 4 to 8.

[0051] Preferably, the metal complex or adduct thereof in this embodiment is a compound represented by the following formula:

[0052] [ka] [ka] [ka] [ka] [ka]

[0053] The method for producing such a metal complex or its adduct is not particularly limited, but an example thereof is a method in which a dicyano compound such as pyridine-2,3-dicarbonitrile and a metal atom are heated in an alcohol solvent in the presence of a basic substance, examples of which include inorganic bases such as potassium carbonate, sodium carbonate, calcium carbonate, sodium bicarbonate, and sodium acetate, and organic bases such as triethylamine, tributylamine, and diazabicycloundecene.

[0054] Here, as the conductive material in such an oxygen reduction catalyst, for example, the following can be used.

[0055] That is, the conductive material is not particularly limited as long as it has conductivity, but examples thereof include carbon materials, metal materials, and metal oxide materials. Furthermore, the conductive material is preferably a carbon material. The conductive material may be used alone or in combination of two or more types.

[0056] The carbon material is preferably derived from conductive carbon. Specific examples of the carbon material include graphite, amorphous carbon, activated carbon, graphene, carbon black, carbon fiber, mesocarbon microbeads, microcapsule carbon, fullerene, carbon nanofoam, carbon nanotube, and carbon nanohorn. Among these, the carbon material is preferably graphite, amorphous carbon, activated carbon, graphene, carbon black, carbon fiber, fullerene, or carbon nanotube, and more preferably carbon nanotube, carbon black, or graphene.

[0057] Examples of carbon nanotubes include single-walled carbon nanotubes (hereinafter referred to as "SWCNT"), double-walled carbon nanotubes (hereinafter referred to as "DWCNT"), and multi-walled carbon nanotubes (hereinafter referred to as "MWCNT").

[0058] The carbon material may contain a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a silicon atom. When the carbon material contains a heteroatom, the carbon material may contain one type of heteroatom alone or two or more types of heteroatoms. The carbon material may be oxidized, hydroxided, nitrided, phosphide, sulfide, or silicided.

[0059] Metallic materials include titanium and tin, and metallic oxide materials include titanium oxide and tin oxide (SnO2, ITO, ATO).

[0060] The conductive material may have a functional group such as a hydroxyl group, a carboxyl group, a nitrogen-containing group, a silicon-containing group, a phosphorus-containing group such as a phosphate group, or a sulfur-containing group such as a sulfonic acid group. In particular, the carbon material preferably has a carboxyl group. When the conductive material has a carboxyl group, the metal complex or an adduct thereof is more easily adsorbed onto the surface of the conductive material, improving the durability of the catalyst and further enhancing the oxygen reduction catalytic activity.

[0061] The conductive material may be surface-treated by oxidation. In particular, oxidation of carbon materials such as carbon black can improve the interaction with the metal complex by adding hydrophilic functional groups such as carboxyl groups and hydroxyl groups, thereby making it possible to control the ionization potential within an optimal range. Known oxidation methods can be used, including wet treatments in which the material is stirred and mixed in an aqueous solution of an oxidizing agent such as nitric acid, sulfuric acid, or chloric acid, and gas-phase treatments such as plasma treatment and ozone treatment.

[0062] When the conductive material contains carboxyl groups, the content of the carboxyl groups is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the conductive material. Having a carboxyl group content equal to or less than the upper limit is advantageous because it reduces the production cost of the catalyst. Furthermore, the carboxyl group content is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. Having a carboxyl group content equal to or greater than the lower limit can further enhance the durability and oxygen reduction catalytic activity of the catalyst. The carboxyl group content can be measured by elemental analysis, X-ray photoelectron spectroscopy, or the like.

[0063] The specific surface area of ​​the conductive material is 0.8m 2 / g or more is preferable, and 10m 2 / g or more is more preferable, and 50m 2 / g or more is more preferable, and 100m 2 / g or more is particularly preferred, and 500m 2 / g or more is most preferable. 2 When the specific surface area is 1 / g or more, it becomes easier to increase the amount of catalyst supported, and the oxygen reduction catalytic activity of the catalyst can be further improved. 2 The specific surface area can be measured by a nitrogen adsorption BET method using a specific surface area measuring device.

[0064] The average particle size of the conductive material is not particularly limited, but is preferably 5 nm to 1000 μm, more preferably 10 nm to 100 μm, and even more preferably 50 nm to 10 μm. Examples of methods for adjusting the average particle size of the conductive material to fall within the above numerical range include the following (A1) to (A3). (A1): A method in which particles are pulverized using a ball mill or the like, and the resulting coarse particles are dispersed in a dispersant to obtain the desired particle size, and then dried and solidified. (A2): A method in which particles are pulverized using a ball mill or the like, and the resulting coarse particles are sieved or the like to select particle size. (A3): A method for optimizing the manufacturing conditions and adjusting the particle size when manufacturing conductive materials. The average particle size can be measured using a particle size distribution measuring device or an electron microscope.

[0065] In the oxygen reduction catalyst of this embodiment, the content of the metal complex or adduct thereof is preferably 75% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, relative to 100% by mass of the total amount of the metal complex or adduct thereof and the conductive material. When the content of the metal complex or adduct thereof is equal to or less than the upper limit, the conductivity of the catalyst is excellent. Furthermore, the content of the metal complex or adduct thereof is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the total amount of the metal complex or adduct thereof and the conductive material. When the proportion of the metal complex or adduct thereof is equal to or more than the lower limit, the oxygen reduction catalytic ability of the catalyst can be further improved.

[0066] [Method of manufacturing concrete devices] Such a concrete device 1 can be manufactured, for example, as follows.

[0067] First, the concrete layer 10 containing the above-mentioned concrete (fresh concrete or solidified concrete) is prepared (formed).

[0068] Next, as shown in Fig. 1, gel layers 121 and 122 are attached and disposed on a pair of end faces of the concrete layer 10. Then, as shown in Fig. 1, electrode 111 is attached and disposed on gel layer 121, and electrode 112 is attached and disposed on gel layer 122. In other words, gel layer 121 and electrode 111 are attached to one end face of the concrete layer 10, and gel layer 122 and electrode 112 are attached to the other end face, in this order.

[0069] Here, the method for manufacturing the electrode 112 is not particularly limited, and the electrode 112 may be manufactured, for example, by applying a liquid composition to the surface of a conductive substrate and removing components other than the catalyst. When removing components other than the catalyst, heat drying may be performed, or pressing may be performed after drying. Alternatively, a catalyst layer may be provided on the surface of the substrate by vacuum deposition or the like. The electrode 112 may have the above-mentioned catalyst layer 112a on only one side of the substrate, or on both sides of the substrate.

[0070] Through the above steps, the concrete device 1 shown in FIG. 1 is completed.

[0071] [Operation, Actions and Effects] Next, the operation, function and effect of the concrete device 1 will be described in detail with reference to FIG. 3 in addition to FIG. 1 and FIG.

[0072] (A. Operation) Figure 3 is a schematic cross-sectional view (ZX cross-sectional view) showing an example of operation of concrete device 1. Figure 3 also shows current I flowing between electrodes 111 and 112 via external wiring 9, and voltage V generated between electrodes 111 and 112 at that time.

[0073] First, as shown in FIG. 3, when wiring 9 is connected between electrodes 111 and 112 in this concrete device 1, the following chemical reaction occurs. Note that in FIG. 3 and in the following chemical formulas, electrons are referred to as "e - " is shown.

[0074] Specifically, on the electrode 111 side (near the interface Sa with the gel layer 121), if the electrode 111 is made of Zn as described above, the following chemical reaction occurs (see FIG. 3). Zn → Zn 2+ +2e - Zn+2Cl - → ZnCl+2e -

[0075] On the other hand, on the electrode 112 side (near the interface Sb with the gel layer 122), if the electrode 112 is made of Cu as described above, the following chemical reaction occurs (see FIG. 3). O2+4H + +4e - → 2H2O O2+2H2O+4e - → 4OH - ·Na + +e - → Na ·Ca 2+ +2e - → Ca Zn 2+ +2e - → Zn

[0076] During such a chemical reaction (reduction reaction, oxidation reaction, etc.), various ions move to the electrode 111 side or the electrode 112 side, for example, as shown in FIG. 3. Specifically, various cations (Ca 2 ,Zn 2+ ,H + ,Na + ) move toward the electrode 112. On the other hand, various anions (Cl - ,OH - ) move toward the electrode 111 side. Then, electrons e - moves from the electrode 111 side to the electrode 112 side, a current I flows from the electrode 112 side to the electrode 111 side via the wiring 9, and a voltage V is generated between the electrodes 111 and 112 (see FIG. 3).

[0077] Furthermore, as the difference in work function between electrodes 111, 112 increases, the current I flowing through concrete device 1 (and the voltage V generated) also increases. In other words, when the difference in work function is relatively small, current I and voltage V also become relatively small, and when the difference in work function is relatively large, current I and voltage V also become relatively large.

[0078] Furthermore, as described above, the gel layers 121, 122 each have the function of improving the ion conduction efficiency between the concrete layer 10 and the electrodes 111, 112 (at the interface), which facilitates the flow of the above-described current I in the concrete device 1. Note that even after the gel layers 121, 122 dry, the ion conduction of the above-described various ions continues.

[0079] Here, as described above, such a concrete device 1 is configured to function as, for example, the following device. That is, the concrete device 1 functions as, for example, a battery (concrete battery) in which the electrode 111 functions as a negative electrode and the electrode 112 functions as a positive electrode. Alternatively, for example, the concrete device 1 functions as a concentration sensor (salt concentration sensor or water concentration sensor) that detects the salt concentration or water concentration in the concrete layer 10.

[0080] When functioning as the above-described salt concentration sensor, the ionic conductivity increases and the amount of current also increases as the salt concentration in the concrete layer 10 increases. Therefore, the salt concentration in the concrete layer 10 can be detected using the value of the current, and therefore the salt concentration in the concrete layer 10 can be measured.

[0081] Furthermore, when functioning as the moisture concentration sensor described above, the ionic conductivity increases and the amount of current also increases as the moisture concentration in the concrete layer 10 increases. Therefore, in the case of this moisture concentration sensor, as in the case of the salt concentration sensor described above, the moisture concentration in the concrete layer 10 can be detected using the value of the current, and therefore the moisture concentration in the concrete layer 10 can be measured.

[0082] (B. Actions and Effects) Here, in the concrete device 1 of the present embodiment, the air electrode containing the oxygen reduction catalyst described above is used as the electrode 112, and thus, for example, the following actions and effects can be obtained.

[0083] That is, first, for example, in the above-mentioned concrete battery as concrete device 1, the output voltage (for example, the voltage V shown in FIG. 3) can be improved (for example, from the conventional level of about 0.8 V to about 1.2 V). In other words, in this embodiment, it is possible to improve the characteristics of concrete device 1.

[0084] It is also possible to provide a plurality of such concrete batteries and connect these batteries in series or in parallel to control the output voltage and current density.

[0085] In addition, in the concrete device 1, as shown in FIG. 3, for example, hydroxide ions (OH - ) is generated, and these hydroxide ions can maintain the alkalinity of the concrete layer 10 (suppress the progress of neutralization). When the concrete layer 10 is neutralized, deterioration generally accelerates, so suppressing the progress of such neutralization can also improve the reliability of the concrete device 1. In other words, such a configuration of the concrete device 1 can be used as a corrosion prevention technology to replace the so-called sacrificial anode method (galva-shield).

[0086] Furthermore, in the concrete device 1 of this embodiment, if the oxygen reduction catalyst in the electrode 112 contains the above-mentioned metal complex or its adduct, it can be a catalyst with excellent oxygen reduction catalytic activity. In addition, since the above-mentioned metal complex or its adduct is easily adsorbed to the above-mentioned conductive material, it is possible to manufacture such an oxygen reduction catalyst without undergoing a complicated manufacturing process. Furthermore, when the above-mentioned metal complex or its adduct is used, excellent oxygen reduction catalytic activity can be obtained without using rare metals such as platinum, so the catalyst can be provided at a relatively low cost.

[0087] Furthermore, in the concrete device 1 of this embodiment, gel layers 121, 122 are provided between the concrete layer 10 (one end surface thereof) and the electrode 111, and between the concrete layer 10 (the other end surface thereof) and the electrode 112, respectively, resulting in the following: In other words, the adhesion and ion conduction efficiency are improved between the concrete layer 10 and the electrodes 111, 112 (interfaces Sa, Sb), and the decrease over time of the current I flowing between the electrodes 111, 112 is suppressed. As a result, it is possible to further improve the characteristics of the concrete device 1 (such as the device's lifespan).

[0088] Furthermore, at least one of these gel layers 121, 122 contains one or more types of ions, resulting in the following: Ion conductivity is improved between the concrete layer 10 and the electrodes 111, 112 (at the interface), increasing the amount of current I, thereby further improving the characteristics of the concrete device 1. Incidentally, as the concentration of ions (ion concentration) contained in the gel layer 121 or 122 increases, the current I flowing through the concrete device 1 (and the generated voltage V) also increases. In other words, when the ion concentration is relatively low, the current I and voltage V are relatively small, respectively. When the ion concentration is relatively high, the current I and voltage V are relatively large, respectively. This is because, as described above, the gel layers 121, 122 also play a role in ion conduction, and therefore, a higher ion concentration in these gel layers 121, 122 further improves the ion conductivity at the interface.

[0089] In addition, these gel layers 121, 122 have the function of improving the ion conduction efficiency between (at the interface) the concrete layer 10 and the electrodes 111, 112, so as described above, it is possible to suppress the decrease in current I over time.

[0090] Furthermore, these gel layers 121, 122 are respectively attached to a pair of end faces of the concrete layer 10, and the electrodes 111, 112 are respectively attached to these gel layers 121, 122, so that the following occurs: That is, since the gel layers 121, 122 and the electrodes 111, 112 can be easily attached, the concrete device 1 can be manufactured easily (at low cost).

[0091] Furthermore, if fresh concrete, for example, is used as the concrete in the concrete layer 10, the amount of current I can be increased, which makes it possible to further improve the characteristics of the concrete device 1. On the other hand, if solidified concrete, for example, is used as the concrete in the concrete layer 10, the concrete layer 10 has a solidified shape, which makes it possible to easily manufacture the concrete device 1.

[0092] <2. Modifications> Next, modifications of the above embodiment (Modifications 1 and 2) will be described. Note that the same components as those in the above embodiment are given the same reference numerals, and descriptions thereof will be omitted where appropriate.

[0093] [Variation 1] FIG. 4 is a schematic diagram showing an example of a cross-sectional configuration (an example of a ZX cross-sectional configuration) of a concrete device (concrete device 1A) according to Modification 1. In FIG.

[0094] The concrete device 1A according to this variant 1 corresponds to the concrete device 1 of the embodiment (see Figure 1) with the following modifications, but the other configurations are the same. That is, as shown in Figure 4, this concrete device 1A has the concrete layer 10 and electrodes 111, 112 described above, and is the concrete device 1 of the embodiment in which the pair of gel layers 121, 122 described above are not provided (omitted).

[0095] In the first modification having such a configuration, basically, it is possible to obtain the same effects as in the above embodiment.

[0096] [Variation 2] FIG. 5 is a schematic diagram showing an example of a cross-sectional configuration (ZX cross-sectional configuration example) of a concrete device (concrete device 1B) according to Modification 2.

[0097] The concrete device 1B according to this modification 2 corresponds to the concrete device 1 (see FIG. 1) of the embodiment, but is modified as follows, and other configurations are the same. That is, in this concrete device 1B, as shown in FIG. 5, a pair of electrodes 1 are provided on one end face (surface) side of the concrete layer 10. 1 1,1 1 Specifically, a pair of gel layers 121 and 122 are disposed (attached) on one end surface of the concrete layer 10, and electrodes 111 and 112 are disposed (attached) on the gel layers 121 and 122, respectively, in a state where they are spaced apart from each other.

[0098] In the second modification having such a configuration, basically, the same effects as those of the embodiment can be obtained.

[0099] As in the case of the above-described modified example 1, in this modified example 2 as well, for example, the pair of gel layers 121 and 122 may not be provided.

[0100] <3. Application Examples> Next, an example of application of the concrete devices (concrete devices 1, 1A, 1B) according to the embodiments and modifications (modifications 1 and 2) described so far to electronic devices will be described.

[0101] 6(A) and 6(B) are block diagrams showing examples of the configuration of electronic devices (electronic devices 2A and 2B) according to the application example.

[0102] First, one concrete device 1 (or one of concrete devices 1A and 1B) is provided in electronic device 2A shown in Fig. 6(A). On the other hand, multiple concrete devices 1 (or one of concrete devices 1A and 1B) (two in this example) are provided in electronic device 2B shown in Fig. 6(B).

[0103] Specific examples of such electronic devices 2A and 2B include various types of sensor devices, communication devices, lighting devices, warning lights, and the like.

[0104] <4. Other Modifications> The technology of the present disclosure has been described above by giving embodiments, modifications, and application examples, but the technology is not limited to these embodiments and can be modified in various ways.

[0105] For example, the configuration (shape, placement position, number, material, etc.) of each component described in the above embodiments is not limited, and other shapes, placement positions, numbers, materials, etc. may be used. Specifically, the above embodiments have basically been described using an example in which at least one of the pair of gel layers 121, 122 contains one or more types of ions, but this example is not limiting. That is, for example, both of the pair of gel layers 121, 122 may not contain one or more types of ions. Furthermore, the above embodiments have been described using an example in which the concrete device is configured as a concrete battery, a salt concentration sensor, or a moisture concentration sensor, but this is not limiting, and the concrete device may be configured as another device.

[0106] In addition, in the above embodiments, specific examples of materials for the oxygen reduction catalyst contained in electrode 112 as the air electrode are given and explained, but the present invention is not limited to the material examples explained in the above embodiments, and other oxygen reduction catalysts may be used. Furthermore, in the above embodiments, specific methods for manufacturing concrete devices are given and explained, but the present invention is not limited to the manufacturing methods explained in the above embodiments, and other methods may be used.

[0107] Furthermore, in the present technology, the contents described above can be applied in any combination.

[0108] The effects described in this specification are merely examples and are not limiting, and other effects may also be present. [Explanation of symbols]

[0109] 1, 1A, 1B... Concrete device, 10... Concrete layer (electrolyte), 111, 112... Electrode, 112a... Catalyst layer, 112b... Current collector layer, 112c... Water-repellent layer, 121, 122... Gel layer (hydrogel layer or ion gel layer), 2A, 2B... Electronic device, 9... Wiring, I... Current, V... Voltage, e - …electron, Sa,Sb…interface.

Claims

1. a concrete layer containing concrete as an electrolyte and having a pair of end surfaces facing each other; a first electrode disposed on one of the pair of end faces of the concrete layer; and a second electrode disposed on one or the other of the pair of end faces of the concrete layer; Equipped with The second electrode is an air electrode containing an oxygen reduction catalyst. Concrete device.

2. The oxygen reduction catalyst contains a metal complex or an adduct thereof represented by the following formula (1) or (2) and a conductive material:

10. The concrete device of claim 1. 【Chemical 1】 (In the formula, M is an iron atom, a manganese atom, a nickel atom, a copper atom, a zinc atom, or a cobalt atom; D1 to D28 each independently represent a nitrogen atom, a sulfur atom, or a carbon atom; When D1 to D28 are carbon atoms, the carbon atoms may each independently be bonded to a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group. However, in the formula (1), when D1 to D16 have 8 or less carbon atoms, At least one of the carbon atoms has a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsulfonyl group, an alkoxy group, or an alkylthio group bonded to it; or The metal complex of the formula (1) forms an adduct.

3. D1 to D16 are nitrogen atoms or carbon atoms.

3. The concrete device of claim 2.

4. D17 to D28 are sulfur atoms or carbon atoms. A concrete device according to claim 2 or claim 3.

5. It is expressed by the following formula: A concrete device according to any one of claims 2 to 4. 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】

6. The metal complex is contained in an amount of 75% by mass or less relative to 100% by mass of the total amount of the metal complex or its adduct and the conductive material. A concrete device according to any one of claims 2 to 5.

7. The conductive material contains a carboxyl group. A concrete device according to any one of claims 2 to 6.

8. The carboxyl group is contained in an amount of 20% by mass or less relative to 100% by mass of the conductive material.

8. The concrete device of claim 7.

9. The oxygen reduction catalyst comprises manganese dioxide, platinum, or a carbon alloy.

10. The concrete device of claim 1.

10. Further provided with one or more gel layers each composed of a hydrogel layer or an ion gel layer between the concrete layer and the first electrode and between the concrete layer and the second electrode. A concrete device according to any one of claims 1 to 9.

11. The concrete in the concrete layer is fresh concrete or hardened concrete. A concrete device according to any one of claims 1 to 10.

12. The first electrode functions as a negative electrode and the second electrode functions as a positive electrode. Alternatively, the concrete battery is configured as a salt concentration sensor that detects the salt concentration in the concrete layer. A concrete device according to any one of claims 1 to 11.

13. one or more concrete devices; The concrete device a concrete layer containing concrete as an electrolyte and having a pair of end surfaces facing each other; a first electrode disposed on one of the pair of end faces of the concrete layer; and a second electrode disposed on one or the other of the pair of end faces of the concrete layer; Equipped with The second electrode is an air electrode containing an oxygen reduction catalyst. electronic equipment.

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