Photo-fuel cell, electrochemical device, and electric power generation method

Abstract

To provide a photo-fuel cell, an electrochemical device, and an electric power generation method, each being excellent in electric power generation sustainability by solving such a problem that a conventional photo-fuel cell uses liquid fuel, and as a result, the conventional photo-fuel cell is difficult to be made smaller and thinner, and a problem that the photo-fuel cell using gaseous fuel tends to lose power generation sustainability over time.SOLUTION: A photo-fuel cell generating electric power using steam as fuel comprises a negative electrode, a positive electrode, an electrochemical device having an electrolyte layer disposed between the negative electrode and the positive electrode, and an external circuit electrically connecting the negative electrode and the positive electrode, and the negative electrode comprises a first photocatalytic layer and a coordination polymer layer, and the positive electrode includes a second photocatalytic layer, the first photocatalytic layer catalyzes a water-splitting reaction when irradiated with light, and the second photocatalytic layer catalyzes an oxygen reduction reaction when irradiated with light.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photo fuel cell that generates electricity using water vapor as fuel, an electrochemical device used in the photo fuel cell, and a power generation method using these.

Background Art

[0002] Conventionally, fuel cells such as polymer electrolyte fuel cells, alkaline electrolyte fuel cells, and phosphoric acid fuel cells have been developed and put into practical use. In recent years, fuel cells using photocatalysts, that is, photo fuel cells, have been proposed. Photo fuel cells can use organic compounds and nitrogen-containing compounds contained in biomass, waste, etc. as fuel, and have attracted attention in terms of effective utilization of resources.

[0003] Patent Document 1 proposes a photo fuel cell in which the photocurrent conversion efficiency is improved by incorporating a redox mediator into a liquid-phase fuel. Patent Document 2 proposes a photo fuel cell in which an organic dye layer is provided in part or all of a photocatalyst layer in contact with a negative electrode layer, thereby increasing the electromotive force.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Incidentally, the invention described in Patent Document 1 uses a liquid-phase fuel containing at least one of an organic compound and a nitrogen-containing compound as the fuel of a photocatalytic fuel cell. Further, the invention described in Patent Document 2 uses liquid water as the fuel. Although the photocatalytic fuel cells according to these prior arts exhibit excellent performance such as electromotive force and photocurrent conversion efficiency, since a liquid material is used as the fuel, it has been difficult to miniaturize and thin them.

[0006] Therefore, an object of the present invention is to provide a photocatalytic fuel cell, an electrochemical device, and a power generation method using novel water vapor as the fuel. Specifically, an object of the present invention is to provide a photocatalytic fuel cell, an electrochemical device, and a power generation method having excellent sustainability of power generation amount. Further, an object of the present invention is to provide a method for manufacturing an electrochemical device having excellent sustainability of power generation amount.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that by using a coordination polymer for the electrodes of a photocatalytic fuel cell, the power generation sustainability of a photocatalytic fuel cell using water vapor as the fuel is improved, and the present invention has been completed.

[0008] That is, the present invention for solving the above problems is A photocatalytic fuel cell that generates power using water vapor as the fuel, comprising a negative electrode, a positive electrode, an electrochemical device having an electrolyte layer disposed between the negative electrode and the positive electrode, and an external circuit that electrically connects the negative electrode and the positive electrode, The negative electrode includes a first photocatalyst layer and a coordination polymer layer, The positive electrode includes a second photocatalyst layer, The first photocatalyst layer catalyzes the decomposition reaction of water by irradiating light, and the second photocatalyst layer catalyzes the reduction reaction of oxygen by irradiating light.

[0009] The photocatalytic fuel cell of the present invention contacts water vapor in the air and irradiates it with light, thereby generating protons and electrons through the decomposition reaction of water. The protons and electrons are conducted to the positive electrode, and the reduction reaction of oxygen proceeds at the positive electrode. Through this reaction, electricity can be extracted. Furthermore, since the photocatalytic fuel cell of the present invention can generate electricity using water vapor as fuel, an electrolytic cell for accommodating a liquid-phase fuel (electrolyte) is unnecessary.

[0010] In addition, the coordination polymer layer is structured by coordination bonds and exhibits excellent radical resistance compared to covalent molecules. Therefore, the photocatalytic fuel cell of the present invention is less likely to undergo photo-degradation and is excellent in the sustainability of the power generation amount.

[0011] In a preferred embodiment of the present invention, the positive electrode further includes a coordination polymer layer. The coordination polymer has high electrochemical stability and is difficult to decompose. Therefore, the coordination polymer has the effect of preventing a decrease in the generated power due to the decomposition of the electrolyte. Therefore, by adopting a configuration in which the positive electrode is provided with a coordination polymer layer, the power generation sustainability can be improved.

[0012] In a preferred embodiment of the present invention, the coordination polymer layer contains a proton-coordinating molecule, an oxoacid ion, and a metal ion, and the oxoacid ion and / or the proton-coordinating molecule contains a coordination polymer coordinated to the metal ion.

[0013] In a preferred embodiment of the present invention, the proton-coordinating molecule is one or more selected from the group consisting of amines, imines, imidazoles, triazoles, benzimidazoles, benzotriazoles, and derivatives thereof.

[0014] In a preferred embodiment of the present invention, the proton-coordinating molecule is a primary amine represented by the general formula R-NH 2 , a secondary amine represented by the general formula R 1 (R 2 )-NH, a general formula R 1 (R2 )(R 3 ) - N represents one or more selected from the group consisting of a tertiary amine, a straight-chain carbon diamine, a saturated cyclic amine, and a saturated cyclic diamine. (R, R 1 , R 2 , R 3 each independently represents any one of an alkyl group, an aryl group, an alicyclic hydrocarbon group, and a heterocyclic group.)

[0015] In a preferred form of the present invention, the metal ion is one or more selected from the group consisting of cobalt ions, copper ions, zinc ions, and gallium ions.

[0016] In a preferred form of the present invention, the oxo acid ion is one or more selected from the group consisting of phosphate ions, hydrogen phosphate ions, and dihydrogen phosphate ions.

[0017] In a preferred form of the present invention, the electrolyte layer is a film containing an acidic group in a polymer such as a fluororesin, or a film of the coordination polymer.

[0018] In a preferred form of the present invention, the negative electrode and the positive electrode further include a conductive layer, and the conductive layer is formed of a conductive nonwoven fabric.

[0019] In a preferred form of the present invention, the negative electrode further includes a moisture absorption layer.

[0020] By configuring the negative electrode to further include a moisture absorption material, water vapor in the air can be captured by the negative electrode. Thereby, the electromotive force of the photo fuel cell can be improved.

[0021] In a preferred form of the present invention, the photo fuel cell further includes a water vapor supply mechanism for supplying water vapor to the negative electrode, and an oxygen supply mechanism for supplying oxygen to the positive electrode.

[0022] In a preferred embodiment of the present invention, the photocatalytic fuel cell is provided with a humidifying mechanism for humidifying the positive electrode. Thereby, the relative humidity on the positive electrode side can be improved, and the electromotive force of the photocatalytic fuel cell can be improved.

[0023] In a preferred embodiment of the present invention, the photocatalytic fuel cell maintains a discharge current within a reduction rate of 20% compared to the maximum value of the discharge current for at least 30 minutes or more after the discharge current reaches the maximum value.

[0024] Further, the present invention for solving the above problems is an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode, wherein the negative electrode includes a first photocatalyst layer and a coordination polymer layer, the positive electrode includes a second photocatalyst layer, and the first photocatalyst layer catalyzes a water decomposition reaction by irradiating light, and the second photocatalyst layer catalyzes an oxygen reduction reaction by irradiating light.

[0025] In a preferred embodiment of the present invention, the positive electrode further includes a coordination polymer layer.

[0026] In a preferred embodiment of the present invention, the negative electrode further includes a moisture absorption layer.

[0027] In a preferred embodiment of the present invention, the thickness from the negative electrode to the positive electrode of the electrochemical device is 0.6 mm or less.

[0028] Further, the present invention for solving the above problems is a power generation method using water vapor as a fuel, comprising a power generation step of irradiating light to the negative electrode and the positive electrode in a photocatalytic fuel cell including an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode to generate power, wherein the negative electrode includes a first photocatalyst layer and a coordination polymer layer, The positive electrode includes a second photocatalyst layer. The power generation process is a power generation method in which, by irradiating light, a reaction for decomposing water proceeds at the negative electrode and a reduction reaction of oxygen proceeds at the positive electrode.

[0029] In a preferred form of the present invention, the power generation method is such that the positive electrode includes a coordination polymer layer and includes a humidification process for humidifying the positive electrode.

[0030] In a preferred form of the present invention, the power generation method further includes a humidity adjustment process for setting the relative humidity of the negative electrode and the positive electrode to 70% RH or less.

[0031] Further, the present invention for solving the above problems is a method for manufacturing an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode, wherein a coordination polymer is disposed on a heated photocatalyst layer, the coordination polymer is melted on the heated photocatalyst layer to make the coordination polymer in an amorphous state, and an electrode creation process for creating an electrode, and includes a joining process for joining the negative electrode, the electrolyte layer, and the positive electrode in this order.

[0032] In a preferred form of the present invention, the electrolyte layer is a film of a coordination polymer, and the joining process includes stacking the negative electrode, the electrolyte layer, and the positive electrode in this order and thermocompression bonding them.

Advantages of the Invention

[0033] According to the present invention, it is possible to provide a novel photocatalytic fuel cell using water vapor as a fuel, an electrochemical device, and a power generation method. Specifically, it is possible to provide a photo fuel cell, an electrochemical device, and a power generation method that use water vapor as fuel and have excellent power generation sustainability. Furthermore, it is possible to provide a method for manufacturing a photo fuel cell and an electrochemical device that have excellent power generation sustainability.

Brief Description of Drawings

[0034]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0035] The present invention relates to a photo fuel cell that generates electricity using water vapor as fuel. FIG. 1 shows the power generation mechanism of the photo fuel cell according to this embodiment. FIG. 2 shows a schematic diagram showing the structure of the electrochemical device 11 according to this embodiment.

[0036] (1) Power Generation Mechanism The photo fuel cell 10 according to this embodiment includes an electrochemical device 11 including a negative electrode 20, a positive electrode 30, and an electrolyte layer 40, and an external circuit 50 that electrically connects the negative electrode 20 and the positive electrode 30.

[0037] The negative electrode 20 includes a first conductive layer 21, a first photocatalyst layer 22, and a first coordination polymer layer 23. The positive electrode 30 includes a second conductive layer 31 and a second photocatalytic layer 32. Further, the positive electrode 30 may be provided with a second coordination polymer layer 33. The first photocatalytic layer 22 contains a photocatalytic component that catalyzes the water decomposition reaction by irradiating light. Specifically, the photocatalytic component is excited by receiving light containing energy equal to or higher than the band gap of the photocatalytic component, and catalyzes the photo-oxidation of water by holes (h + ) according to the following formula 1.

[0038] 2H 2 O + 4h + → O 2 + 4H + + 4e - ···(Formula 1)

[0039] The photocatalytic component contained in the first photocatalytic layer 22 is excited by receiving light, and the electrons in the valence band are excited to the conduction band to become first excited electrons. The valence band that has lost an electron becomes a state with a monovalent hole (h + ). By this hole taking electrons from water molecules, the oxidation reaction from water to oxygen proceeds, and the hole combines with the taken electrons and disappears. On the other hand, the first excited electrons are supplied to the positive electrode 30 through the external circuit.

[0040] On the other hand, the second photocatalytic layer 32 contains a photocatalytic component that catalyzes the reduction reaction of oxygen by irradiating light. Specifically, the photocatalytic component is excited by receiving light containing energy equal to or higher than the band gap of the photocatalyst, and catalyzes the photoreduction of oxygen in the presence of protons and oxygen according to the following formula 2.

[0041] O 2 + 4H + + 4e - → 2H 2 O ···(Formula 2)

[0042] The photocatalytic component in the second photocatalytic layer 32 is excited by receiving light, and the electrons in the valence band become third excited electrons in the conduction band. The valence band that has lost an electron is a monovalent hole (h +It enters a state with , and this hole recombines with the electrons supplied from the negative electrode through the external circuit 50 and disappears. The third excited electron has a strong reducing power, and 4e on the left side of the above formula 2 - becomes and reduces oxygen.

[0043] As the light for irradiation, light in the wavelength range of 200 nm to 800 nm, that is, light near the ultraviolet-visible light region can be used. Also, sunlight including light of these wavelengths may be used. That is, it becomes possible to generate electricity with light near the ultraviolet-visible light region. The light source may use an external light source outside the configuration of the photo fuel cell (including natural light, indoor light such as fluorescent lamps and LEDs), or may be provided with a light source as a configuration of the photo fuel cell. As the light source, an LED, a halogen lamp, a xenon lamp, etc. can be used.

[0044] (2) Electrochemical device The electrochemical device 11 according to this embodiment includes the negative electrode 20, the positive electrode 30, and the electrolyte layer 40 as described above. The electrochemical device 11 is preferably a membrane-electrode assembly (MEA).

[0045] Examples of the photocatalyst component contained in the first photocatalyst layer 22 of the negative electrode 20 include metal oxides such as titanium oxide, tungsten oxide, tin oxide, zinc oxide, niobium oxide, iron oxide, and bismuth oxide, composite metal oxides such as bismuth vanadate, metal nitrides such as gallium nitride, metal phosphides such as gallium phosphide, and metal sulfides such as cadmium sulfide. The photocatalyst component in the present invention is preferably titanium oxide.

[0046] Examples of the photocatalyst component contained in the second photocatalyst layer 32 of the positive electrode 30 include metal oxides such as bismuth oxychloride, titanium oxide, tungsten oxide, tin oxide, zinc oxide, niobium oxide, iron oxide, and bismuth oxide, composite metal oxides such as bismuth vanadate, metal nitrides such as gallium nitride, metal phosphides such as gallium phosphide, and metal sulfides such as cadmium sulfide, nanoparticle-supported n-type semiconductors such as Pt-TiO 2 and Ag-TiO 2 etc., and BiOCl, CaFe 2O 4 , ZnMn 2 O 4 , InP, AgGaS 2 Examples of p-type semiconductors include the above.

[0047] The loading amount of the photocatalyst component is not particularly limited, but is preferably 0.3 g / cm 2 or more, more preferably 1 g / cm 2 or more, more preferably 1.5 g / cm 2 or more, even more preferably 2 g / cm 2 or more, particularly preferably 3 g / cm 2 or more. Also, the loading amount of the photocatalyst component is preferably 5 g / cm 2 or less, more preferably 4.5 g / cm 2 or less, even more preferably 4 g / cm 2 or less, particularly preferably 3.8 g / cm 2 or less, most preferably 3.5 g / cm 2 or less. By setting the loading amount within the above range, the discharge current (μA) of the photocatalytic fuel cell can be increased.

[0048] The first conductive layer 21 and the second conductive layer 31 may be formed of a material that conducts electricity (electrons). Examples of such materials include metals such as gold, platinum, silver, iron, copper, nickel, aluminum, titanium, and cobalt, and carbon materials such as activated carbon, carbon nanotubes, and fullerenes.

[0049] The first conductive layer 21 and the second conductive layer 31 are preferably porous structures. More preferably, they are fibrous or particulate. The first conductive layer 21 and the second conductive layer 31 are preferably formed of a conductive nonwoven fabric. Examples of the conductive nonwoven fabric include titanium nonwoven fabric. The shapes of the first conductive layer 21 and the second conductive layer 31 are preferably thin layer-like or plate-like. With such a configuration, the photocatalyst layer can be brought into contact with water vapor serving as fuel.

[0050] The thickness of the conductive layer, particularly the first conductive layer 21, is preferably 50 μm or more, more preferably 60 μm or more, still more preferably 70 μm or more, particularly preferably 80 μm or more, and most preferably 90 μm or more. Also, the thickness of the conductive layer, particularly the first conductive layer 21, is preferably less than 300 μm, more preferably 250 μm or less, still more preferably 200 μm or less, further more preferably 150 μm or less, particularly preferably 130 μm or less, and most preferably 110 μm or less. By setting the thickness of the conductive layer within the above range, the discharge current (μA) of the photo fuel cell can be increased. Also, the photo fuel cell or the electrochemical device can be miniaturized.

[0051] The first coordination polymer layer 23 and the second coordination polymer layer 33 have proton conductivity. That is, the coordination polymer layer can conduct protons generated by the photooxidation reaction. The shapes of the first coordination polymer layer 23 and the second coordination polymer layer 33 are preferably thin layer-like or plate-like.

[0052] Here, the coordination polymer layer 23 and the coordination polymer layer 33 contain a coordination polymer. The coordination polymer contains a proton-coordinating molecule, an oxo acid ion, and a metal ion. The coordination polymer preferably has a structure in which a proton-coordinating molecule and / or an oxo acid ion is coordinated to a metal ion.

[0053] Examples of the proton-coordinating molecule preferably include molecules having two or more ligand sites for coordinating protons in the molecule. Examples include imidazole, triazole, benzimidazole, benzotriazole, and their derivatives. Here, the derivative means a compound in which a part of the chemical structure is replaced by another atom or atomic group. Specific examples include 2-methylimidazole, 2-ethylimidazole, histamine, histidine, etc. with respect to imidazole. These molecules have ligand sites with an excellent balance between proton coordination and release, and are excellent in ion conductivity.

[0054] Also, as the proton-coordinating molecule, preferably, a primary amine represented by the general formula R-NH 2 , a secondary amine represented by the general formula R 1 (R 2 )-NH, and a tertiary amine represented by the general formula R 1 (R 2 )(R 3 )-N are exemplified. Here, R, R 1 , R 2 , R 3 are each independently any one of an alkyl group, an aryl group, an alicyclic hydrocarbon group, and a heterocyclic group.

[0055] Examples of such primary amines include lower alkylamines such as methylamine, ethylamine, and propylamine, and aromatic amines such as aniline and toluidine. Examples of the secondary amine include di-lower alkylamines such as dimethylamine, diethylamine, and dipropylamine, and aromatic secondary amines such as N-methylaniline and N-methyltoluidine.

[0056] As the tertiary amine, preferably, those in which at least one or more of the above R 1 , R 2 , R 3 are alkyl groups are exemplified. More preferably, those in which all of the above R 1 , R 2 , R 3 are alkyl groups are exemplified. Even more preferably, those in which all of the above R 1 , R 2 , R 3 are linear alkyl groups are exemplified. Also, the tertiary amine preferably includes a short-chain alkyl group and a long-chain alkyl group as the above R 1 , R 2 , R 3 . Particularly preferably, those containing at least two or more long-chain alkyl groups are exemplified. Here, as the long-chain alkyl group, preferably those having 4 or more carbon atoms in the main chain can be mentioned. More preferably, those having 5 or more, preferably 6 or more, preferably 7 or more, and particularly preferably 8 carbon atoms can be mentioned. As a guideline for the upper limit, those having 12 carbon atoms can be mentioned. As the short-chain alkyl group, preferably those having 3 or less carbon atoms in the main chain can be mentioned. More preferably, those having 2 or less, and particularly preferably 1 carbon atom can be mentioned. Examples of such a tertiary amine include N-methyl-N,N'-dioctylamine.

[0057] Examples of the oxo acid ion include phosphate ion, sulfate ion, etc. From the chemical stability to hydrogen, preferably it is a phosphate ion. The phosphate ion may be in the form of a hydrogen phosphate ion with one proton coordinated, or a dihydrogen phosphate ion with two protons coordinated. The oxo acid ion in the present invention is coordinated to the metal ion in the form of a monomer that has not undergone condensation, for example, whereby the proton concentration is maintained in a high state and the stability to moisture is also excellent.

[0058] As the metal ion, preferably high-period transition metal ions and typical metal ions can be mentioned. Preferably, transition metal ions and typical metal ions of the 4th period can be mentioned. Examples include cobalt ion, copper ion, zinc ion, and gallium ion. More preferably, it is a zinc ion. The metal ion is not particularly limited as long as it easily forms a coordination bond with the oxo acid ion and / or the proton-coordinating molecule.

[0059] Here, the metal ion and the oxo acid ion preferably form at least one or more chemical bonds. Preferably, at least one oxo acid ion is chemically bonded to the metal ion. More preferably, a plurality of oxo acid ions are chemically bonded. In addition, ligands other than oxo acid ions such as water molecules may be bonded to the metal ion. The chemical bonds between metal ions and oxoacid ions can include, but are not limited to, coordination bonds and covalent bonds.

[0060] The ratios of metal ions, oxoacid ions, and proton-coordinating molecules contained in the coordination polymer are preferably such that, for 1 metal ion, there are 1 to 4 oxoacid ions and 1 to 3 proton-coordinating molecules. By setting the ratios within the above numerical ranges, the stability of the coordination polymer can be improved. More preferably, for 1 metal ion, there are 3 oxoacid ions and 1 proton-coordinating molecule.

[0061] Preferred examples of the coordination polymer include those having a structure in which phosphate ions are coordinated to zinc ions. More preferably, those in which dihydrogen phosphate ions and hydrogen phosphate ions are each coordinated are included. Particularly preferably, those in which at least two or more dihydrogen phosphate ions are coordinated to zinc ions are included. Also, preferred examples of the coordination polymer include those in which proton-coordinating molecules are coordinated to those in which phosphate ions are coordinated to zinc ions. Preferably, those in which amines or imidazoles are coordinated as proton-coordinating molecules to those in which phosphate ions are 3-coordinated to zinc ions are included. Particularly preferably, those in which tertiary amines are coordinated as proton-coordinating molecules are included. As an example, [Zn(HPO 4 )(H 2 PO 4 ) 2 (C 8 H 17 ) 2 NCH 3 (hereinafter referred to as ZnPMdoa), [Zn(HPO 4 )(H 2 PO 4 ) 2 (ImH 2 ) 2 (hereinafter referred to as ZnPIm), etc. are included.

[0062] Coordination polymers can be appropriately selected from the substances exemplified as the above metal ions, oxo acid ions, and proton-coordinating molecules according to the intended use and then generated. A coordination polymer can be obtained, for example, by mixing and stirring a raw material containing a metal ion, an oxo acid, a proton-coordinating molecule, and an additive. Also, for the mixing and stirring, all the raw materials may be mixed and stirred at once. Preferably, the raw material containing a metal ion and the oxo acid are mixed and stirred, and then the proton-coordinating molecule is added to the obtained stirred mixture and mixed and stirred again. Examples of the raw material containing the metal ion preferably include a simple metal, a compound containing a metal ion, or a metal oxide.

[0063] When preparing a coordination polymer, the mixing ratio of the raw material containing a metal ion, an oxo acid, and a proton-coordinating molecule is preferably 1 to 4 mmol of the oxo acid and 1 to 3 mmol of the proton-coordinating molecule with respect to 1 mmol of the raw material containing a metal ion. More preferably, with respect to 1 mmol of the raw material containing a metal ion, there are 3 mmol of the oxo acid and 1 mmol of the proton-coordinating molecule.

[0064] Here, although it will be described in detail in the item of (4) manufacturing method, in the present invention, the coordination polymer layer can be produced by heating and melting a coordination polymer body and molding it into a film shape. Note that the coordination polymer body means a material composed of a coordination polymer. Examples of the shape of the coordination polymer body include pellets, coordination polymer pieces, powders, and the like.

[0065] In the present invention, the coordination polymer layer is preferably composed of a coordination polymer in an amorphous state.

[0066] The mass ratio of the photocatalyst to the coordination polymer contained in the negative electrode and the positive electrode is preferably 5 to 18 of the coordination polymer with respect to 1 of the photocatalyst.

[0067] The electrolyte layer 40 is not particularly limited as long as it has proton conductivity (ionic conductivity). The electrolyte layer is preferably a solid polymer membrane. As the electrolyte layer, the above-described coordination polymer formed in a film shape can be used. Preferably, an amorphous coordination polymer formed in a film shape can be used. Alternatively, a film containing a sulfuric acid group, a sulfonic acid group, a carboxy group, or the like in a polymer such as a fluororesin can be used. Examples of the perfluorosulfonic acid membrane having a sulfonic acid group include Nafion membrane, Flemion) membrane, Aciplex membrane, Aquivion membrane, Dow membrane, and the like.

[0068] When using a coordination polymer as the electrolyte layer, the coordination polymer can be heated and melted, and mechanical energy can be applied from above and pressed to form a film for use.

[0069] The thickness of the electrolyte layer is preferably 50 μm or more, more preferably 60 μm or more, still more preferably 70 μm or more, particularly preferably 80 μm or more, and most preferably 90 μm or more. Also, the thickness of the conductive layer, particularly the first conductive layer 21, is preferably less than 300 μm, more preferably 250 μm or less, still more preferably 200 μm or less, still more preferably 150 μm or less, particularly preferably 130 μm or less, and most preferably 110 μm or less.

[0070] The first coordination polymer layer 23 and the first photocatalyst layer 22 are preferably configured such that water vapor moves from the first coordination polymer layer 23 to the first photocatalyst layer. Preferably, the first coordination polymer layer 23 and the first photocatalyst layer 22 are configured to be in contact with each other. The first photocatalyst layer 22 and the first conductive layer 21 are preferably configured such that protons generated in the first photocatalyst layer 22 move to the first conductive layer 21. Preferably, the first photocatalyst layer 22 and the first conductive layer 21 are configured to be in contact with each other. The first conductive layer 21 and the electrolyte layer 40 are preferably configured such that protons that have moved from the first photocatalyst layer 22 move from the first conductive layer 21 to the electrolyte layer 40. Preferably, the first conductive layer 21 and the electrolyte layer 40 are configured to be in contact with each other. The electrolyte layer 40 and the second conductive layer 31 are preferably configured such that protons move from the electrolyte layer 40 to the second conductive layer 31. Preferably, the electrolyte layer 40 and the second conductive layer 31 are configured to be in contact with each other. The second conductive layer 31 and the second photocatalytic layer 32 are preferably configured such that protons move from the second conductive layer 31 to the second photocatalytic layer 32. Preferably, the second conductive layer 31 and the second photocatalytic layer 32 are configured to be in contact with each other. The second photocatalytic layer 32 and the second coordination polymer layer 33 are preferably configured such that water vapor moves from the second coordination polymer layer 33 to the second photocatalytic layer 32. Preferably, the second photocatalytic layer 32 and the second coordination polymer layer 33 are configured to be in contact with each other.

[0071] The negative electrode 20 preferably has the first conductive layer 21, the first photocatalytic layer 22, and the first coordination polymer layer 23 laminated in this order from the electrolyte layer 40. The positive electrode 30 preferably has the second conductive layer 31, the second photocatalytic layer 32, and the second coordination polymer layer 33 laminated in this order from the electrolyte layer 40. Preferably, it has a structure in which electrons and protons generated by the reaction are efficiently delivered to their respective conductive layers starting from the photocatalyst.

[0072] The relationship between the cross-sectional areas of the conductive layer, the photocatalytic layer, and the coordination polymer layer constituting the electrode is not particularly limited. As an example, a configuration example of the negative electrode 20 including the conductive layer 21, the photocatalytic layer 22, and the coordination polymer layer 23 is shown in FIG. 3. Also, the configuration of the electrode may be in a form in which the layers constituting the electrode are enlarged in the order of the first conductive layer 21, the first coordination polymer layer 23, and the first photocatalytic layer 22.

[0073] Also, the negative electrode 20 and the positive electrode 30 may include a moisture absorption layer. Preferably, the moisture absorption layer may be provided so as to be in contact with the photocatalytic layers 22 and 32. The moisture absorption layer has proton conductivity and hygroscopicity. Therefore, the moisture absorption layer can capture water vapor serving as fuel in the electrodes (negative electrode and positive electrode) and conduct protons generated by the photooxidation reaction. Examples of the moisture absorption layer include porous materials. For example, porous materials can be used. Preferably, mesoporous materials are used, and more preferably, hydrophilic mesoporous materials. Examples include porous silica and hydrophilic porous carbon. In addition, for example, ionomers can be used. An ionomer is a polymer having an acidic functional group, and examples of the acidic functional group include a sulfonic acid group, a phosphonic acid group, and a carboxyl group. Examples of ionomers include perfluorosulfonic acid ionomers such as Nafion (registered trademark, hereinafter omitted), Flemion (registered trademark, hereinafter omitted), Flemion (registered trademark, hereinafter omitted), and Aquivion (registered trademark, hereinafter omitted).

[0074] (3) Photo fuel cell The photo fuel cell 10 according to this embodiment includes the above-described electrochemical device 11 and an external circuit 50 that electrically connects the negative electrode 20 and the positive electrode 30.

[0075] The photo fuel cell of the present invention preferably further includes a water vapor supply mechanism that supplies water vapor to the negative electrode. As one embodiment of the water vapor supply mechanism, there is a mechanism in which an inert gas is bubbled through water to obtain a saturated water vapor gas, and the saturated water vapor gas is introduced into the negative electrode. Examples of the inert gas include nitrogen gas and argon gas.

[0076] The device configuration for realizing one embodiment of the water vapor supply mechanism is shown in FIG. 4. Examples of the configuration include an inert gas filling unit 60 such as a gas cylinder or a gas capsule filled with an inert gas, a water filling unit 62 filled with liquid water, an inert gas flow path 61 that connects the inert gas filling unit and the water filling unit and supplies the inert gas to the water filling unit, and a saturated water vapor gas flow path 63 that connects the water filling unit and the negative electrode chamber 24 and supplies the saturated water vapor gas to the negative electrode chamber 24. Water vapor that was not consumed in the oxidation reaction of the negative electrode and oxygen generated by the oxidation reaction of the negative electrode are exhausted through the negative electrode exhaust flow path 64.

[0077] The photo fuel cell of the present invention preferably further includes an oxygen supply mechanism that supplies oxygen to the positive electrode. As one embodiment of the oxygen supply mechanism, it can be configured to include an oxygen gas filling part filled with oxygen gas or pseudo-air gas (oxygen concentration of about 20%), and an oxygen gas flow path connecting the oxygen gas filling part and the positive electrode chamber.

[0078] Further, the photo fuel cell of the present invention preferably further includes a humidifying mechanism for supplying and humidifying water vapor to the positive electrode. As a humidifying mechanism on the positive electrode side, an example can be a mechanism that bubbles the oxygen gas or the like into water and fills the positive electrode chamber. A specific configuration is shown in FIG. 4. As such a configuration, the oxygen gas filling part 70, a water filling part 72 filled with liquid water, an oxygen gas flow path 71 connecting the oxygen gas filling part 70 and the water filling part 72 and supplying oxygen gas to the water filling part, and a saturated water vapor gas flow path 73 connecting the water filling part 72 and the positive electrode chamber 34 and supplying saturated water vapor gas of oxygen gas to the positive electrode chamber 34 can be exemplified. By supplying water vapor to the positive electrode side, the relative humidity is improved, and the electromotive force of the photo fuel cell can be increased. Oxygen that has not been consumed by the reduction reaction of the positive electrode, air other than oxygen, and water generated by the reduction reaction are exhausted from the positive electrode exhaust flow path 74.

[0079] Further, the photo fuel cell of the present invention preferably includes a humidity adjustment mechanism for adjusting the relative humidity of the negative electrode and the positive electrode. From the viewpoint of ensuring the power generation amount of the photo fuel cell, the lower limit of the relative humidity of the negative electrode and the positive electrode adjusted by the humidity adjustment mechanism is preferably 40% RH or more, 50% RH or more, 60% RH or more. Also, from the viewpoint of preventing deterioration of the photo fuel cell, depending on the characteristics of the coordination polymer employed, a form in which the relative humidity of the negative electrode and the positive electrode is 100% RH or less, 80% RH or less, 70% RH or less is also preferable.

[0080] Also, as another embodiment of the humidifying mechanism and the oxygen supply mechanism, an air supply mechanism that takes in air into the negative electrode accommodating portion (for example, the negative electrode chamber 24) that accommodates the negative electrode, or the positive electrode accommodating portion (for example, the positive electrode chamber 34) that accommodates the positive electrode can be exemplified. In this embodiment, water vapor in the air can be utilized at the negative electrode, and oxygen in the air can be utilized at the positive electrode. Further, at the positive electrode, the relative humidity can be increased by utilizing water vapor in the air.

[0081] In this embodiment, a structure having an air introduction portion for taking in air into the photo fuel cell and an air circulation portion for circulating the air inside the photo fuel cell can be exemplified. The air introduction portion only needs to be able to introduce outside air into the accommodating portion that accommodates the negative electrode or the positive electrode. For example, a ventilation port can be exemplified. Further, the air introduction portion is preferably provided with a filter in order to prevent the introduction of dust, dirt, etc. in the outside air into the photo fuel cell.

[0082] Examples of the air circulation portion include a fan and a small circulator.

[0083] In this embodiment, a circulation-type photo fuel cell can be provided in which the oxygen generated on the negative electrode side is supplied to the positive electrode side, and the water (water vapor) generated on the positive electrode side is supplied to the negative electrode side. By adopting such a form, the entire photo fuel cell can be miniaturized.

[0084] The positive electrode accommodating portion and the negative electrode accommodating portion are preferably composed of a material having at least partial light transmissibility. That is, the positive electrode accommodating portion and the negative electrode accommodating portion preferably have the property of transmitting the light necessary for the reaction by the photocatalyst. Specifically, the light transmittance of the light necessary for the reaction by the photocatalyst is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and particularly preferably 80% or more. Examples of such a material include glass (quartz).

[0085] Although not shown in the figure, each flow path is preferably provided with a check valve (one-way valve) in order to prevent the backflow of the gas.

[0086] The photocatalytic fuel cell of the present invention, as an electrochemical device, may use a stack in which the electrochemical devices are stacked. The stack can be manufactured by a conventional method. For example, a separator may be provided on the negative electrode side and / or the positive electrode side of an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer existing between the negative electrode and the positive electrode, and the electrochemical devices may be further stacked with the separator interposed therebetween.

[0087] The photocatalytic fuel cell of the present invention maintains a discharge current within a reduction rate of 20% or less compared to the maximum value of the discharge current for at least 30 minutes or more after the discharge current reaches the maximum value. Preferably, it can be maintained for 1 hour or more, 10 hours or more, 20 hours or more, 30 hours or more, 40 hours or more. Here, the discharge current of the photocatalytic fuel cell can be measured using a source meter (Model "2450" manufactured by Keithley Instruments, Inc.).

[0088] (4) Method for manufacturing an electrochemical device An example of the method for manufacturing the electrochemical device of the present invention will be described below. However, the method for manufacturing the electrochemical device of the present invention is not limited to the following. is not limited to the following.

[0089] (4-1) Preparation of photocatalyst component slurry First, a photocatalyst component and water are put into a mixer mill container and subjected to the mixer mill to prepare a slurry of the photocatalyst component for the first photocatalyst layer (negative electrode) and a slurry of the photocatalyst component for the second photocatalyst layer (positive electrode). As the photocatalyst component used for the first photocatalyst layer and the photocatalyst component used for the second photocatalyst layer, those described in (2) can be used.

[0090] The ratio of the photocatalyst component to water varies depending on the type of the photocatalyst component and the target loading amount, but the water can be 1 to 20 parts by mass, 3 to 20 parts by mass, 5 to 20 parts by mass, 5 to 15 parts by mass, or 7 to 12 parts by mass with respect to 1 part by mass of the photocatalyst component.

[0091] (4-2) Formation of conductive layer and photocatalyst layer Mask one side of the material for forming the conductive layer (e.g., titanium non-woven fabric), dip-coat it in the slurry of the photocatalyst component described in (4-1), and dry it. After drying, remove the masking tape and sinter it to obtain a negative electrode and a positive electrode having a conductive layer and a photocatalyst layer.

[0092] The drying temperature is not particularly limited, and it is dried at about 80 to 120 °C. The drying time varies depending on the drying temperature. For example, when drying at 100 °C, it is dried for about 3 to 4 hours.

[0093] For sintering, appropriate sintering temperature and sintering time may be selected according to the type of the photocatalyst component. For example, when the photocatalyst component is TiO 2 or AgTiO 2 in this case, the sintering temperature can be set to 300 °C or higher and the sintering time can be set to 1 hour or longer.

[0094] (4-3) Formation of the coordination polymer layer Heat the negative electrode or positive electrode having a conductive layer and a photocatalyst layer on a hot plate, and place a coordination polymer on top of the photocatalyst layer. The placed coordination polymer melts and becomes an amorphous state, and is coated in a layer on top of the photocatalyst layer. Thereby, a negative electrode or positive electrode in which a conductive layer, a photocatalyst layer, and a coordination polymer layer are laminated in this order can be obtained. The state of the coordination polymer before being placed on the photocatalyst layer is not particularly limited. The coordination polymer obtained in a crystalline state may be placed. Also, the coordination polymer obtained in an amorphous state may be placed.

[0095] The heating temperature of the negative electrode or positive electrode having a conductive layer and a photocatalyst layer is not particularly limited. Preferably, it is 100 to 190 °C. The state of the coordination polymer placed on top of the photocatalyst layer is not particularly limited, and examples include a crystalline state and an amorphous state.

[0096] (4-4) Fabrication of an electrochemical device (membrane-electrode assembly) First, stack the negative electrode fabricated in (4-3), the electrolyte layer, and the positive electrode fabricated in (4-3) in this order on a Teflon (registered trademark) plate, and then stack another Teflon (registered trademark) plate on top of them. From above the stacked Teflon (registered trademark) plates, perform heat-pressing. After finishing the heat-pressing, remove the negative electrode, the electrolyte layer, and the positive electrode together with the Teflon (registered trademark) plates from the heat-pressing machine and allow them to cool. After finishing the cooling, recover the electrochemical device (membrane-electrode assembly) composed of the negative electrode, the electrolyte layer, and the positive electrode from the Teflon (registered trademark) plate.

[0097] The temperature of the heat-pressing is not particularly limited and can be, for example, 120 to 160 °C. The time of the heat-pressing varies depending on the temperature but can be, for example, about 1 to 10 minutes.

[0098] Here, when the electrolyte layer in (4-4) is a coordination polymer, the film of the coordination polymer can be manufactured by the following procedure. First, heat and melt the coordination polymer on a polyimide film. Transfer the melted coordination polymer onto a Teflon (registered trademark) plate and press it from above to obtain a film of the coordination polymer.

[0099] The heating temperature of the coordination polymer is not particularly limited. Appropriate heating temperature and heating time can be selected according to the type of the coordination polymer. Also, the temperature when heating the coordination polymer is not particularly limited and can be, for example, 120 to 160 °C. Further, the time of the pressing varies depending on the temperature but can be, for example, about 1 to 10 minutes.

Example

[0100] (Test Example 1) Fabrication of Electrochemical Device · Preparation of Coordination Polymer Zinc oxide (1 mmol, 81 mg) and phosphoric acid aqueous solution (3 mmol, 210 μL) were mixed and stirred for 15 minutes. An aqueous solution of Mdoa (N-methyl-Ndioctylamine, 1 mmol, 320 μL) was mixed and stirred into the obtained mixture to obtain a white, paste-like substance. It was dried at room temperature for 12 h and further dried in a vacuum dryer at 120 °C for 3 h to obtain an amorphous form of ZnPMdoa.

[0101] · Preparation of electrolyte layer ZnPMdoa was melted at 190 °C and melted on a polyimide film. 300 mg of melted and amorphous ZnPMdoa was placed on a PTFE film and pressed at 160 °C under a condition of 0.6 N for 10 minutes.

[0102] · Preparation of electrodes 0.6 g of titanium oxide (TiO 2 ) and 6 mL of water were put into a mixer mill container (10 mL) and subjected to a mixer mill (25 Hz, 45 minutes) to prepare a titanium oxide slurry for the negative electrode. Also, 0.6 g of silver titanium oxide (AgTiO 2 , Ag: 3 wt%) and 6 mL of water were put into a mixer mill container (10 mL) and similarly subjected to a mixer mill to prepare a silver titanium oxide slurry for the positive electrode.

[0103] Next, two pieces of titanium non-woven fabric (manufactured by Nichibo Techno Co., fiber diameter: 20 μm, size: 12 mm square, thickness: 100 μm, porosity 33%) with one side masked were prepared and dip-coated with the titanium oxide slurry for the negative electrode or the silver titanium oxide slurry for the positive electrode, respectively. Next, the dip-coated titanium non-woven fabric was dried at 100 °C for about 3 to 4 hours. After drying, the masking tape was peeled off and sintered in a sintering furnace at 300 °C for 1 hour to fabricate TiO 2 / Ti non-woven fabric (for negative electrode), AgTiO 2 / Ti non-woven fabric (for positive electrode).

[0104] TiO 2A coordination polymer composed of ZnPMdoa was placed on a TiO / Ti non-woven fabric (for the negative electrode), and ZnPMdoa was melted. The melted ZnPMdoa in an amorphous state was applied to the TiO / Ti non-woven fabric (for the negative electrode) to fabricate a negative electrode. The same operation was performed on an AgTiO / Ti non-woven fabric (for the positive electrode) to fabricate a positive electrode. 2 / Ti non-woven fabric (for the negative electrode) to fabricate a negative electrode. 2 / Ti non-woven fabric (for the positive electrode) to fabricate a positive electrode.

[0105] · Fabrication of an electrochemical device The negative electrode, electrolyte layer, and positive electrode were stacked in this order on a press machine and heat-pressed at 140 °C and 0.45 N for 10 minutes under vacuum conditions to obtain the electrochemical device of this example. The configuration of the electrochemical device of this example is shown in Table 1.

[0106]

Table 1

[0107] (Test Example 2) Confirmation of power generation sustainability A photo fuel cell was fabricated with the same configuration as shown in Fig. 4. Specifically, the negative electrode and positive electrode of the electrochemical device fabricated in Test Example 1 were connected by an external circuit. The negative electrode was placed in a negative electrode chamber supplied with an Ar-saturated water vapor gas, and the positive electrode was placed in a positive electrode chamber supplied with an oxygen gas-saturated water vapor gas. An Ar-saturated water vapor gas was supplied to the negative electrode chamber, and an oxygen gas-saturated water vapor gas was supplied to the positive electrode chamber. Light irradiation was performed on both electrodes using a solar simulator ("HAL-320W" manufactured by Asahi Spectra Co., Ltd.). The discharge current of the photo fuel cell of Example 1 was measured using a source meter ("Model 2450" manufactured by Keithley Instruments, Inc.). The results are shown in Fig. 5.

[0108] In Test Example 2, light irradiation was performed on the photo fuel cell of this example for 70 hours or more from the start of measurement (the gray part in the figure). The photo fuel cell of this example was capable of generating power for 70 hours or more from the start of measurement by light irradiation. Also, after the discharge current reached the maximum value, a discharge current within 20% of the decrease rate from the maximum value of the discharge current was maintained for 40 hours or more.

[0109] Next, 72.5 hours after the start of light irradiation, the light irradiation was stopped for about one hour, and then the light irradiation was performed again. The measured values of the discharge current during this period are shown in FIG. 6. In Test Example 2, even when the light irradiation was stopped once and then restarted, the discharge current equivalent to that before the stop was measured. From the above results, it was found that the power generation amount of the photocatalytic fuel cell continues even when the stop and restart of the light irradiation are repeated.

Industrial Applicability

[0110] The present invention can be applied to batteries for small devices such as smartphones.

Explanation of Signs

[0111] 10 Photocatalytic fuel cell 11 Electrochemical device 20 Negative electrode 21 First conductive layer 22 First photocatalyst layer 23 Coordination polymer layer (negative electrode) 24 Negative electrode chamber 30 Positive electrode 31 Second conductive layer 32 Second photocatalyst layer 33 Coordination polymer layer (positive electrode) 34 Positive electrode chamber 40 Electrolyte layer 50 External circuit 60 Inert gas filling part 61 Inert gas flow path 62 Water filling part (negative electrode) 63 Saturated water vapor gas flow path (negative electrode) 64 Exhaust flow path (negative electrode) 70 Oxygen gas filling part 71 Oxygen gas flow path 72 Water filling part (positive electrode) 73 Saturated water vapor gas flow path (positive electrode) 74 Exhaust flow path (positive electrode)

Claims

1. An optoelectrochemical cell comprising a negative electrode, a positive electrode, an electrolyte layer disposed between the negative electrode and the positive electrode, and an external circuit electrically connecting the negative electrode and the positive electrode, the optoelectrochemical cell generating electricity using water vapor as a fuel, wherein the negative electrode includes a first photocatalyst layer and a coordination polymer layer, the positive electrode includes a second photocatalyst layer, the first photocatalyst layer catalyzes a water decomposition reaction upon irradiation with light, and the second photocatalyst layer catalyzes an oxygen reduction reaction upon irradiation with light.

2. The optoelectrochemical cell according to claim 1, wherein the positive electrode further includes a coordination polymer layer.

3. The optoelectrochemical cell according to claim 1 or 2, wherein the coordination polymer layer contains a proton-coordinating molecule, an oxoacid ion, and a metal ion, and includes a coordination polymer in which the oxoacid ion and / or the proton-coordinating molecule coordinates to the metal ion.

4. The optoelectrochemical cell according to claim 3, wherein the proton-coordinating molecule is at least one selected from the group consisting of amines, imines, imidazoles, triazoles, benzimidazoles, benzotriazoles, and derivatives thereof.

5. The proton-coordinating molecule is a primary amine represented by the general formula R-NH ２ , a secondary amine represented by the general formula R １ (R ２ )-NH, a tertiary amine represented by the general formula R １ (R ２ )(R ３ )-N, a linear-chain carbon diamine, a saturated cyclic amine, and a saturated cyclic diamine, and is at least one selected from the group consisting of these, the photo fuel cell according to claim 3. (R, R １ , R ２ , R ３ each independently represents any one of an alkyl group, an aryl group, an alicyclic hydrocarbon group, and a heterocyclic group.)

6. The optoelectrochemical cell according to claim 3, wherein the metal ion is at least one selected from the group consisting of cobalt ions, copper ions, zinc ions, and gallium ions.

7. The optoelectrochemical cell according to claim 3, wherein the oxoacid ion is at least one selected from the group consisting of phosphate ions, hydrogen phosphate ions, and dihydrogen phosphate ions.

8. The optoelectrochemical cell according to claim 1 or 2, wherein the electrolyte layer is a film containing an acidic group in a polymer such as a fluororesin, or a film of the coordination polymer.

9. The negative electrode and the positive electrode further include a conductive layer, and the conductive layer is formed of a conductive nonwoven fabric.

10. The optoelectrochemical cell according to claim 1 or 2, wherein the negative electrode further includes a moisture absorption layer.

11. Furthermore, a water vapor supply mechanism for supplying water vapor to the negative electrode, and an oxygen supply mechanism for supplying oxygen to the positive electrode.

12. The optoelectrochemical cell according to claim 2, further including a humidifying mechanism for humidifying the positive electrode.

13. The optoelectrochemical cell, for at least 30 minutes or more after the discharge current reaches its maximum value, The photocatalytic fuel cell according to claim 1 or 2, characterized in that a discharge current with a reduction rate within 20% is maintained as compared with the maximum value of the discharge current.

14. An electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode, wherein the negative electrode includes a first photocatalyst layer and a coordination polymer layer, the positive electrode includes a second photocatalyst layer, the first photocatalyst layer catalyzes a water decomposition reaction by irradiating light, and the second photocatalyst layer catalyzes an oxygen reduction reaction by irradiating light, an electrochemical device.

15. The electrochemical device according to claim 14, wherein the positive electrode further includes a coordination polymer layer.

16. The electrochemical device according to claim 14 or 15, wherein the negative electrode further includes a moisture absorption layer.

17. The electrochemical device according to claim 14 or 15, wherein the thickness from the negative electrode to the positive electrode of the electrochemical device is 0.6 mm or less.

18. A power generation method using water vapor as a fuel, comprising a power generation step of irradiating light to the negative electrode and the positive electrode in a photocatalytic fuel cell including an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode to generate power, wherein the negative electrode includes a first photocatalyst layer and a coordination polymer layer, the positive electrode includes a second photocatalyst layer, in the power generation step, by irradiating light, a reaction for decomposing water proceeds at the negative electrode, and a reduction reaction of oxygen proceeds at the positive electrode, a power generation method.

19. wherein the positive electrode includes a coordination polymer layer, and the power generation method according to claim 18, comprising a humidifying step of humidifying the positive electrode.

20. Furthermore, the power generation method according to claim 19, having a humidity adjustment step of setting the relative humidity of the negative electrode and the positive electrode to 70% RH or less.

21. A method for manufacturing an electrochemical device having a negative electrode, a positive electrode, and an electrolyte layer disposed between the negative electrode and the positive electrode, disposing a coordination polymer on a heated photocatalyst layer, melting the coordination polymer on the heated photocatalyst layer to make the coordination polymer in an amorphous state, and an electrode creating step of creating an electrode, A method for manufacturing an electrochemical device, including a joining step of joining the negative electrode, the electrolyte layer, and the positive electrode in this order.

22. The electrolyte layer is a film of a coordination polymer. The bonding step includes laminating the negative electrode, the electrolyte layer, and the positive electrode in this order and thermocompression bonding them, the method for manufacturing an electrochemical device according to claim 21.

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