JP6566509B2 - Fuel cell - Google Patents
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- JP6566509B2 JP6566509B2 JP2014242685A JP2014242685A JP6566509B2 JP 6566509 B2 JP6566509 B2 JP 6566509B2 JP 2014242685 A JP2014242685 A JP 2014242685A JP 2014242685 A JP2014242685 A JP 2014242685A JP 6566509 B2 JP6566509 B2 JP 6566509B2
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- 239000000446 fuel Substances 0.000 title claims description 36
- 239000011941 photocatalyst Substances 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003014 ion exchange membrane Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 37
- 239000002253 acid Substances 0.000 description 26
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 25
- 229910001882 dioxygen Inorganic materials 0.000 description 25
- 239000007789 gas Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910010413 TiO 2 Inorganic materials 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- -1 alkyne alkene Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
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- 238000007872 degassing Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
Description
本発明は、燃料電池に関するものであり、より具体的には、光触媒を用いた燃料電池に関するものである。 The present invention relates to a fuel cell, and more specifically to a fuel cell using a photocatalyst.
燃料電池とは、燃料の酸化反応を用いることにより電気を取り出すことのできる電池であり、一般に、酸素と燃料の水素の反応を用いて電気を取り出すものであって、重金属等を使う他の化学電池に比べ地球環境に優しく、現在も活発に研究開発が行われている。 A fuel cell is a cell that can take out electricity by using an oxidation reaction of fuel, and generally takes out electricity by using a reaction between oxygen and hydrogen of fuel, and uses other chemicals that use heavy metals. It is friendly to the global environment compared to batteries, and research and development are still underway.
燃料電池において、光エネルギーを用いてより効率的に電気を取り出そうとする試みがなされており、例えば下記特許文献１に、光触媒を用いた燃料電池が開示されている。 Attempts have been made to extract electricity more efficiently by using light energy in fuel cells. For example, Patent Document 1 below discloses a fuel cell using a photocatalyst.
特許文献１に記載の燃料電池では、安定的・持続的に電力を発生させるためにはアノード電解液内に発生した酸素を脱気するための光燃料電池外部からの窒素ガス供給が必要となる。また、カソード電極反応用に光燃料電池外部からの酸素ガス供給が必要である。窒素ガス、酸素ガスを供給しない場合、時間が経過すると光燃料電池の発電性能が低下してしまうため、性能の低下を避けるために窒素ガス、酸素ガスを供給する必要があり、光燃料電池に窒素ガス、酸素ガスを供給するための複雑な機構を設けなければならず、また、窒素ガス、酸素ガスの供給の手間がかかるという課題があった。 In the fuel cell described in Patent Document 1, in order to generate electric power stably and continuously, it is necessary to supply nitrogen gas from the outside of the optical fuel cell for degassing oxygen generated in the anode electrolyte. . In addition, oxygen gas supply from the outside of the photofuel cell is required for the cathode electrode reaction. If nitrogen gas and oxygen gas are not supplied, the power generation performance of the photofuel cell will deteriorate over time, so it is necessary to supply nitrogen gas and oxygen gas to avoid a decrease in performance. A complicated mechanism for supplying nitrogen gas and oxygen gas has to be provided, and there is a problem that it takes time to supply nitrogen gas and oxygen gas.
そこで、本発明は上記課題に鑑み、酸素ガスと窒素ガスを供給しなくても発電性能の低下が少なく性能が持続する、光触媒を用いた燃料電池を提供することを目的とする。 In view of the above-described problems, an object of the present invention is to provide a fuel cell using a photocatalyst that maintains the performance with little decrease in power generation performance without supplying oxygen gas and nitrogen gas.
上記課題を解決するために、本発明の一つの観点によれば、燃料電池を、酸水溶液と、酸水溶液に浸され、かつ、外部回路に電気的に接続されるアノード電極と、外部回路に電気的に接続され、かつ、酸水溶液に浸されるカソード電極と、アノード電極と前記カソード電極の間に配置されたイオン交換膜と、アノード電極の表面に配置され、光が照射されているときに水を分解する光触媒と、酸水溶液、アノード電極、カソード電極及び光触媒を収容し、少なくとも一部が光透過性を有する収容部材とを有し、アノード電極側の酸水溶液の上に有機化合物を有するものとする。前記有機化合物は、アルカン、アルキンアルケン又は、アルケンアルキン、エーテル、芳香属化合物、ハロゲン化アルカン、ハロゲン化アルケン又はハロゲン化アルキンとすると望ましい。また、前記有機化合物をヘキサンとするとより望ましい。 In order to solve the above-described problems, according to one aspect of the present invention, a fuel cell includes an acid aqueous solution, an anode electrode immersed in the acid aqueous solution and electrically connected to an external circuit, and an external circuit. A cathode electrode that is electrically connected and immersed in an acid aqueous solution, an ion exchange membrane that is disposed between the anode electrode and the cathode electrode, and a surface that is disposed on the surface of the anode electrode and is irradiated with light. A photocatalyst for decomposing water, and an acid aqueous solution, an anode electrode, a cathode electrode, and a photocatalyst, and at least a part of the light transmissive accommodating member, and an organic compound on the acid aqueous solution on the anode electrode side Shall have. The organic compound is preferably alkane, alkyne alkene, alkene alkyne, ether, aromatic compound, halogenated alkane, halogenated alkene or halogenated alkyne. More preferably, the organic compound is hexane.
さらに、前記有機化合物を、アノード電極側の前記酸水溶液よりも酸素の溶解度が高いものとすると望ましい。 Furthermore, it is desirable that the organic compound has higher oxygen solubility than the acid aqueous solution on the anode electrode side.
また、本発明の他の観点によれば、燃料電池を、酸水溶液と、酸水溶液に浸され、かつ、外部回路に電気的に接続されるアノード電極と、外部回路に電気的に接続され、かつ、酸水溶液に浸されるカソード電極と、アノード電極とカソード電極の間に配置されたイオン交換膜と、アノード電極の表面に配置され、光が照射されているときに水を分解する光触媒と、酸水溶液、アノード電極、カソード電極及び光触媒を収容し、少なくとも一部が光透過性を有する収容部材とを有し、イオン交換膜が気孔を有するものとした。さらに、前記気孔に一方向弁を設けると望ましい。 According to another aspect of the present invention, a fuel cell is electrically connected to an acid aqueous solution, an anode electrode immersed in the acid aqueous solution and electrically connected to an external circuit, and the external circuit; And a cathode electrode immersed in an acid aqueous solution, an ion exchange membrane disposed between the anode electrode and the cathode electrode, a photocatalyst disposed on the surface of the anode electrode and decomposing water when irradiated with light, In addition, an acid aqueous solution, an anode electrode, a cathode electrode, and a photocatalyst are accommodated, and at least a part of the accommodating member has light permeability, and the ion exchange membrane has pores. Furthermore, it is desirable to provide a one-way valve in the pore.
外部から酸素ガス、窒素ガスを供給する必要のない光触媒を用いた燃料電池を提供することができる。 A fuel cell using a photocatalyst that does not need to supply oxygen gas and nitrogen gas from the outside can be provided.
以下、本発明の実施形態について説明する。ただし、本発明は多くの異なる形態による実施が可能であり、以下に示す実施形態の例示に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. However, the present invention can be implemented in many different forms, and is not limited to the following exemplary embodiments.
図１は、本実施形態に係る燃料電池１（以下「本電池」ということがある。）の概略を示す図である。本電池１は、酸水溶液２と、窒素ガス３a又は酸素ガス３bと、酸水溶液２中に浸される一対の電極４a（アノード電極）、４b（カソード電極）と、酸水溶液２中の水を分解する光触媒（光が照射されているときに触媒作用を示す物質）５a（アノード側光触媒）、５b（カソード側光触媒）と、酸水溶液２、窒素ガス又は酸素ガス３、一対のアノード電極４a、カソード電極４b、アノード側光触媒５a、カソード側光触媒５bを収容し、少なくとも一部が透過性を有する部材で構成される収容部材６とを有する。本電池１は、一対の電極を電子部品を介して導線により接続することで一対の電極間に電気を流すことができる。ここで、アノードとは、外部回路から電流が流れ込む電極のことをいい、カソードとは、外部回路へ電流が流れ出す電極（言い換えると、外部回路から電子が流れ込む電極）をいう。 FIG. 1 is a diagram showing an outline of a fuel cell 1 (hereinafter sometimes referred to as “the present battery”) according to the present embodiment. The battery 1 includes an acid aqueous solution 2, a nitrogen gas 3a or an oxygen gas 3b, a pair of electrodes 4a (anode electrode) and 4b (cathode electrode) immersed in the acid aqueous solution 2, and water in the acid aqueous solution 2. Decomposing photocatalyst (substance that exhibits catalytic action when irradiated with light) 5a (anode-side photocatalyst), 5b (cathode-side photocatalyst), acid aqueous solution 2, nitrogen gas or oxygen gas 3, a pair of anode electrodes 4a, And a housing member 6 that houses the cathode electrode 4b, the anode-side photocatalyst 5a, and the cathode-side photocatalyst 5b, and at least a part of which is made of a permeable member. In the battery 1, electricity can flow between the pair of electrodes by connecting the pair of electrodes with a conductive wire via an electronic component. Here, the anode refers to an electrode through which current flows from an external circuit, and the cathode refers to an electrode from which current flows into the external circuit (in other words, an electrode through which electrons flow from the external circuit).
本実施形態において酸水溶液２は、酸を含み酸性を示す水溶液をいう。酸性とすることで、水溶液内でプロトンがかかわる化学反応を速めるといった効果がある。pHとしては、上記効果を達成することができる限りにおいて限定されるわけではないが、6以下であることが好ましく、より好ましくは２以上５以下の範囲である。 In this embodiment, the acid aqueous solution 2 refers to an aqueous solution containing an acid and showing acidity. By making it acidic, there is an effect of accelerating a chemical reaction involving protons in an aqueous solution. The pH is not limited as long as the above effect can be achieved, but is preferably 6 or less, more preferably 2 or more and 5 or less.
また、本実施形態において、酸水溶液２に含まれる酸としては、本実施形態の効果を達成することができる限りにおいて限定されるわけではないが、例えば塩酸、硫酸、硝酸、リン酸、炭酸、フッ酸、ホウ酸、シュウ酸、クエン酸、アスコルビン酸等を挙げることができる。とりわけ、酸水溶液の濃度を変化させることが容易な、強酸性の塩酸、硫酸、硝酸が好適である。酸水溶液２は、水溶液中の水が光触媒によって分解される際に生ずる電子を外部回路８に供給するのに対応してプロトン（水素イオン）をもう一方の電極触媒に伝達するのに必要な物質である。 In the present embodiment, the acid contained in the acid aqueous solution 2 is not limited as long as the effect of the present embodiment can be achieved. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, Examples include hydrofluoric acid, boric acid, oxalic acid, citric acid, and ascorbic acid. In particular, strongly acidic hydrochloric acid, sulfuric acid, and nitric acid that can easily change the concentration of the aqueous acid solution are preferable. The acid aqueous solution 2 is a substance necessary for transmitting protons (hydrogen ions) to the other electrode catalyst in response to supplying electrons generated when water in the aqueous solution is decomposed by the photocatalyst to the external circuit 8. It is.
また、本実施形態において、酸素ガス３bは、プロトン及び電子と反応して水となり、一対の電極間に電気を流すのに必要な物質である。 In the present embodiment, the oxygen gas 3b reacts with protons and electrons to become water, and is a substance necessary for flowing electricity between a pair of electrodes.
本実施形態において一対の電極４a、４bは、酸水溶液２中に浸されるとともに、水溶液中の光が光触媒によって分解される際に生じる電子を外部回路に供給する一方、外部回路を経由して戻ってきた電子が電極４内において、酸水溶液２からイオン交換膜７を通過したプロトン及び酸素ガスと反応して水を発生させる。本実施形態に係る電極４の材料としては、上記機能を有する限りにおいて限定されるわけではないが、C（Carbon）、ITO（Indium Tin Oxide）、FTO（Fluorine Tin Oxide）、TO（Tin Oxide）等を含んだものを採用することができる。なお、ITO等の薄膜を電極として用いる場合、石英およびパイレック（登録商標）スガラス等の基板上に付することが好ましい。 In the present embodiment, the pair of electrodes 4a and 4b is immersed in the acid aqueous solution 2 and supplies electrons generated when the light in the aqueous solution is decomposed by the photocatalyst to the external circuit, while passing through the external circuit. The returned electrons react with protons and oxygen gas that have passed through the ion exchange membrane 7 from the acid aqueous solution 2 in the electrode 4 to generate water. The material of the electrode 4 according to the present embodiment is not limited as long as it has the above function, but C (Carbon), ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide), TO (Tin Oxide) The thing containing etc. can be employ | adopted. In addition, when using thin films, such as ITO, as an electrode, it is preferable to apply | coat on substrates, such as quartz and Pyrex (trademark) glass.
また、本実施形態においてアノード側の光触媒５aは、光が照射されることによって水溶液中の水を分解することができるものであり、より具体的には水を酸素、プロトン、電子に分解させるものである。本実施形態に係るアノード側の光触媒５aの例としては、上記機能を有する限りにおいて限定されるわけではないが、WO3、TiO2、SnO及びZnOの少なくともいずれかを含むものであることが好ましい。これらは200nm以上700nm以下の範囲の光の波長領域において上記分解活性を十分に発揮することができ、とりわけ紫外可視領域近傍の光で発電することが可能となる。 In the present embodiment, the anode-side photocatalyst 5a is capable of decomposing water in the aqueous solution when irradiated with light, more specifically, decomposing water into oxygen, protons, and electrons. It is. An example of the anode-side photocatalyst 5a according to the present embodiment is not limited as long as it has the above function, but preferably contains at least one of WO 3 , TiO 2 , SnO, and ZnO. These can sufficiently exhibit the above-described decomposition activity in the wavelength region of light in the range of 200 nm or more and 700 nm or less, and in particular, can generate power with light in the vicinity of the ultraviolet-visible region.
本実施形態における光触媒による反応について説明する。本電池では、アノードで水を光分解して水素イオン（プロトン）を得て、カソードでその水素イオンを化学反応させる。この際の両極間での電子の移動を電力として得る。具体的には、水溶液に浸したアノード電極光触媒５aに紫外可視光を照射すると、光触媒内に励起電子と正孔（ホール、ｈ＋）が発生する。この正孔が消費されることで、水が酸素とプロトンとに分解されて（下記反応式（１））、電子（e−）が過剰の状態になる。この電子が外部回路を通過し、反応（１）で生じたプロトンが酸水溶液及び膜を伝わり、それぞれカソードに到達する。カソード電極光触媒５bの選択により、例えばプロトンを酸素と反応させ、水に戻すことができる（下記反応式（２））。また、プロトンと電子との反応により水素ガスとして取り出すこともできる（下記反応式（３））。
２H2O＋４ｈ＋→O２＋４H＋（１）
O2＋４H＋＋４e−→２H２O（２）
２H＋＋２e−→H2 （３）
The reaction by the photocatalyst in this embodiment will be described. In this battery, water is photolyzed at the anode to obtain hydrogen ions (protons), and the hydrogen ions are chemically reacted at the cathode. At this time, the movement of electrons between the two poles is obtained as electric power. Specifically, when ultraviolet visible light is irradiated to the anode electrode photocatalyst 5a immersed in an aqueous solution, excited electrons and holes (holes, h + ) are generated in the photocatalyst. By consuming these holes, water is decomposed into oxygen and protons (the following reaction formula (1)), and the electrons (e − ) become excessive. The electrons pass through the external circuit, and protons generated in the reaction (1) travel through the acid aqueous solution and the membrane to reach the cathode, respectively. By selecting the cathode electrode photocatalyst 5b, for example, protons can be reacted with oxygen and returned to water (the following reaction formula (2)). Moreover, it can also take out as hydrogen gas by reaction with a proton and an electron (following Reaction formula (3)).
2H 2 O + 4h + → O 2 + 4H + (1)
O 2 + 4H + + 4e − → 2H 2 O (2)
2H + + 2e − → H 2 (3)
また、本実施形態において、光触媒は、上記電極の両方の上に形成されていることが好ましい。電極上に光触媒を配置すると、電極に極めて近い位置で光触媒反応を起こし、水を酸素とプロトンに分解させる一方、電子を外部回路に供給させやすくなる。また、光触媒をカソード側においても配置することが好ましい。カソード側に電極上に配置することで外部回路経由で伝達してきた電子が光触媒内に取り込まれやすくなり、その結果酸素ガスの還元反応がより促進されるという効果がある。本実施形態に係るカソード側の光触媒５bの例としては、上記機能を有する限りにおいて限定されるわけではないが、WO3、n型半導体（固体内に電子ドナーを含む半導体）、例えばTiO2、ZnO、BiOCl、CaFe2O4、ZnMn2O4、InP、AgGaS2又はナノ粒子担持n型半導体、例えばTiO2、ZnO、BiOCl、CaFe2O4、ZnMn2O4、InP、AgGaS2の少なくともいずれかを含むものであることが好ましいが、これに限定されるものではない。ここでより仕事関数（表面から電子を取り出すのに必要なエネルギー）が大きい金属のナノ粒子に接した担持ｎ型半導体は、金属ナノ粒子に流れた電子は逆に戻りにくくなり、整流作用を示すことでカソードにおいて円滑に光還元作用を示すと考えることができる。一方、各種ｐ型半導体では水溶液との界面においてバンドが低い（プラスの）エネルギー側に曲がるため、カソードに用いた場合には水溶液中に電子を移行させやすく、やはり円滑に光還元作用を示すといえる。 In the present embodiment, the photocatalyst is preferably formed on both of the electrodes. When a photocatalyst is disposed on the electrode, a photocatalytic reaction occurs at a position very close to the electrode, and water is decomposed into oxygen and protons, while electrons are easily supplied to an external circuit. Moreover, it is preferable to arrange the photocatalyst also on the cathode side. By disposing on the electrode on the cathode side, the electrons transmitted via the external circuit are easily taken into the photocatalyst, and as a result, the reduction reaction of oxygen gas is further promoted. Examples of the cathode-side photocatalyst 5b according to the present embodiment are not limited as long as they have the above functions, but are WO 3 , an n-type semiconductor (a semiconductor including an electron donor in a solid), for example, TiO 2 , ZnO, BiOCl, CaFe 2 O 4 , ZnMn 2 O 4 , InP, AgGaS 2 or nanoparticle-supported n-type semiconductor, such as TiO 2 , ZnO, BiOCl, CaFe 2 O 4 , ZnMn 2 O 4 , InP, AgGaS 2 Although it is preferable that any of them is included, it is not limited to this. Here, the supported n-type semiconductor in contact with the metal nanoparticles having a larger work function (energy necessary for extracting electrons from the surface) makes it difficult for the electrons flowing to the metal nanoparticles to return to the opposite direction and exhibits a rectifying action. Thus, it can be considered that the photoreduction action is smoothly exhibited at the cathode. On the other hand, in various p-type semiconductors, the band bends to the low (plus) energy side at the interface with the aqueous solution. I can say that.
また、本実施形態において、収容部材６は、上記のとおり、酸水溶液２、窒素ガス又は酸素ガス３、一対の電極４及び光触媒５を収容し、少なくとも一部が透過性を有する部材で構成されている。ここでいう透過性とは、光触媒による反応に必要な光のうち６０％以上透過させるものをいい、より具体的には、上記200nm以上700nm以下の波長範囲にある光のうち６０％以上透過させるものをいい、より好ましくは７０％、さらに好ましくは８０％以上である。本実施形態に係る収容部材の材料としては、上記機能を有し、酸水溶液や酸素ガスと不要な反応をしない限りにおいて限定されるわけではないが、例えば金属やガラス等を用いることが好ましい。なお、この透過性を有する部材近傍に、電極を配置することが反応効率の観点から好ましい。 In the present embodiment, as described above, the housing member 6 contains the acid aqueous solution 2, the nitrogen gas or the oxygen gas 3, the pair of electrodes 4 and the photocatalyst 5, and at least a part thereof is made of a permeable member. ing. The term “transmittance” as used herein refers to light that is transmitted by 60% or more of the light required for the reaction by the photocatalyst, and more specifically, light that is in the wavelength range of 200 nm to 700 nm is transmitted 60% or more. More preferably 70%, still more preferably 80% or more. The material of the housing member according to the present embodiment is not limited as long as it has the above function and does not cause unnecessary reaction with the acid aqueous solution or oxygen gas, but for example, metal or glass is preferably used. In addition, it is preferable from a viewpoint of reaction efficiency to arrange | position an electrode near the member which has this permeability | transmittance.
また、本電池は、一対の電極の間に配置され、収容部材を分けるイオン交換膜７を有する。このイオン交換膜７は、異符号のイオンの通過を阻止し、同符号のイオンのみを通過させる性質を持ち、材料としては、上記機能を有する限りにおいて限定されるわけではないが、フッ素樹脂等の高分子中に、硫酸基、スルホン酸基やカルボキシル基等を含んだものを採用することができる。例えば、スルホン酸基を含むナフィオン（Nafion）膜を用いることができる。ナフィオンとは、スルホ化されたテトラフルオロエチレンを基にしたフッ素樹脂の共重合体であり、陰イオンや電子は膜内を移動せず陽イオンだけ移動するポリマーである。なお、このイオン交換膜７によって収納部材６の内部は２つに分割されることとなり、一方で水から酸素とプロトンが、他方からプロトンと酸素の反応によって水を得るものであるため、一方に酸素ガスを、他方に非酸化性のガス（例えばヘリウムガス、窒素ガス、アルゴンガス）等を充填させることが好ましい。このイオン交換膜７は、イオンの効率的な移動のために設けられている。 Moreover, this battery has the ion exchange membrane 7 which is arrange | positioned between a pair of electrodes and divides an accommodating member. This ion exchange membrane 7 has the property of blocking the passage of ions with different signs and allowing only the ions with the same signs to pass through. The material is not limited as long as it has the above functions, but is not limited to fluororesin, etc. A polymer containing a sulfuric acid group, a sulfonic acid group, a carboxyl group, or the like can be used. For example, a Nafion membrane containing a sulfonic acid group can be used. Nafion is a fluororesin copolymer based on sulfonated tetrafluoroethylene, and is a polymer in which anions and electrons move only in the cation without moving in the membrane. The ion exchange membrane 7 divides the inside of the housing member 6 into two parts. On the one hand, oxygen and protons are obtained from water, and water is obtained from the other by the reaction of protons and oxygen. It is preferable to fill the other side with oxygen gas and non-oxidizing gas (for example, helium gas, nitrogen gas, argon gas) or the like. The ion exchange membrane 7 is provided for efficient movement of ions.
本電池は、光燃料電池内に生じた酸素ガスを循環させることにより、外部からのガス供給の必要のない、完全に独立して発電することができるものである。 This battery can generate electricity completely independently without the need for external gas supply by circulating oxygen gas generated in the photofuel cell.
本電池は、アノード電解液上に、アノード電解液の界面に接するように、酸素溶解層９を有し、プロトン伝導膜７に気孔１０を有している。酸素溶解層９は、例えば液体の有機化合物を含有する層とする。アノード反応で生成した酸素は電解液中に溶解する。溶解した酸素は、酸素の溶解度の違いに基づく分配に基づき、電解液（塩酸水溶液）よりも酸素溶解層９へと優先的に移動する。酸素溶解層９内に溶解した酸素は、溶解平衡によりアノード気相へ徐々に脱気され、さらに本電池でのアノード反応（ガス生成）とカソード反応（ガス消費）の圧力差により、プロトン伝導膜７の気孔１０を通過してカソード気相へと移動する。カソード気相に達した酸素は溶解平衡によりカソード電解液へ溶解する。この一連の仕組みにより、酸素ガスが光燃料電池内部で循環する光燃料電池を実現した。気孔１０を設けなくても酸溶液２へ飽和溶解した酸素ガスおよび酸素ガス3bにより本電池の発電は可能であるが、気孔を設けた方がより多くの量の酸素をカソード気相に移動させることができる。プロトン伝導膜７の気孔１０の大きさは特に限定はされないが、大きすぎると気孔における気流の方向が安定せず、小さすぎると酸素ガスの移動量が不十分となるため、気孔の大きさは、5mm以上20mm以下とすることが好ましい。また、気孔を通過する酸素ガスの方向を一定とするために、気孔にふたのような形状の一方向弁を設けることが好ましい。 This battery has an oxygen-dissolved layer 9 on the anode electrolyte so as to be in contact with the interface of the anode electrolyte, and has a pore 10 in the proton conductive membrane 7. The oxygen-dissolving layer 9 is a layer containing, for example, a liquid organic compound. Oxygen produced by the anodic reaction dissolves in the electrolyte. The dissolved oxygen moves preferentially to the oxygen-dissolving layer 9 over the electrolytic solution (aqueous hydrochloric acid solution) based on the distribution based on the difference in solubility of oxygen. Oxygen dissolved in the oxygen-dissolving layer 9 is gradually deaerated into the anode gas phase by dissolution equilibrium, and further, due to the pressure difference between the anode reaction (gas generation) and the cathode reaction (gas consumption) in this battery, the proton conducting membrane 7 passes through the pores 10 and moves to the cathode gas phase. Oxygen that has reached the cathode gas phase is dissolved in the cathode electrolyte by dissolution equilibrium. With this series of mechanisms, we have realized a photovoltaic fuel cell in which oxygen gas circulates inside the photovoltaic fuel cell. Even if the pores 10 are not provided, the battery can generate power with the oxygen gas 3b saturated with the acid solution 2 and the oxygen gas 3b. However, if the pores are provided, a larger amount of oxygen is transferred to the cathode gas phase. be able to. The size of the pores 10 of the proton conducting membrane 7 is not particularly limited, but if it is too large, the direction of the air flow in the pores is not stable, and if it is too small, the amount of movement of oxygen gas becomes insufficient. The thickness is preferably 5 mm or more and 20 mm or less. In order to make the direction of oxygen gas passing through the pores constant, it is preferable to provide a one-way valve shaped like a lid in the pores.
本電池は、アノード反応で生成した酸素が内部循環することで、外部からの生成酸素脱気のための窒素の供給やカソード反応のための酸素の供給を不要とする、完全に独立して発電することが可能な光燃料電池である。そのため、ガス供給のためのボンベ等が必要なくなり、光燃料電池が小型化でき、さらにメンテナンス無しで無人の長期の発電が可能となる。 This battery completely circulates the oxygen generated in the anode reaction, eliminating the need for supplying nitrogen for degassing the oxygen generated from the outside and supplying oxygen for the cathode reaction. It is a photovoltaic fuel cell that can be used. This eliminates the need for gas supply cylinders and the like, enables the photofuel cell to be downsized, and enables unattended long-term power generation without maintenance.
本電池の酸素溶解層９の材料については、液体の有機化合物であれば特に限定はされないが、アルカン、アルケン、アルキンが適しており、アルカンの中では例えばn−ヘキサン（C6H14）が適している。また、液体の有機化合物でなくても、アノード電解液よりも酸素溶解度が高い物質で酸素溶解層９を構成すれば、酸素循環の効果を得ることができる。 The material of the oxygen-dissolving layer 9 of this battery is not particularly limited as long as it is a liquid organic compound, but alkanes, alkenes, and alkynes are suitable. Among the alkanes, for example, n-hexane (C 6 H 14 ) is used. Is suitable. Even if it is not a liquid organic compound, the oxygen circulation effect can be obtained if the oxygen-dissolved layer 9 is made of a material having a higher oxygen solubility than the anode electrolyte.
１．実施例１：ガス外部供給型光燃料電池
ガス外部供給型光燃料電池の概略図を図２に示す。以下、図１と同じ部分は説明を省略する。両側に石英窓が付いたパイレックス（登録商標）ガラス容器６の中央をイオン交換膜であるプロトン伝導性高分子膜７で仕切って反応セルとした。容器（反応セル）６の両側にpH 2の塩酸水溶液２を加え、ITO（インジウムスズ酸化物）-TiO2電極４a及びITO-Ag/TiO2電極４bを、それぞれの水溶液２に浸した。さらに両電極を結線した図３の回路を構成した。ITO-TiO2電極４a及びITO-Ag/TiO2電極４bに、それぞれ窒素、酸素ガスを毎分100mLの速度でバブルさせながら流通させ、さらに両電極に480Wアーク灯から光照射した。30分間光照射した後、光照射を30分間停止した。ガスは流通させたままとした。このon/offサイクルを5回繰り返し、回路に流れる電流の変化をモニターした。光照射に対応した生成電流が確認され、光照射のサイクルを重ねるにつれ生成電流密度値が36.8μA/cm2から50.7μA/cm2まで上昇した（図４）。ここで光触媒層の面積はいずれも1.3 cm2であった。
さらに、図５のように回路を組み替え、可変抵抗を500kΩから0.3Ωに変化させながら電流-電圧特性を測定したところ、図7に示す曲線を得た。開放電圧は1.59Vと求められた（表1）。
Further, when the circuit was rearranged as shown in FIG. 5 and the current-voltage characteristics were measured while changing the variable resistance from 500 kΩ to 0.3Ω, the curve shown in FIG. 7 was obtained. The open circuit voltage was determined to be 1.59V (Table 1).
２．実施例２：ガス閉鎖型光燃料電池
ガス閉鎖型光燃料電池の概略を図６に示す。以下、図１と同じ部分の説明は省略する。実施例1と同様の容器（反応セル）６の両側にpH 2の塩酸水溶液２を加え、ITO-TiO2電極４a及びITO-Ag/TiO2電極４bを、それぞれの水溶液２に浸した。さらに両電極を結線した回路（図３）を構成した。ITO-TiO2電極４a及びITO-Ag/TiO2電極４bに、それぞれ窒素、酸素ガスを毎分100mLの速度でバブルさせながら1時間流通させた。それぞれのガスの供給を止め、セルを密封した後、両電極に480 Wアーク灯から光照射した。30分間光照射した後、光照射を30分間停止した。このon/offサイクルを7回繰り返し、回路に流れる電流の変化をモニターした。1サイクル目の生成電流密度値は26.7 μA/cm2であり、3サイクル目まで電流密度値が上昇し27.5μA/cm2に達した。その後のサイクルでは生成電流が減少していき、7サイクル目では25.0μA/cm2となった。ここで光触媒層の面積はいずれも1.3 cm2であった。
2. Example 2: Gas closed type photo fuel cell An outline of a gas closed type photo fuel cell is shown in FIG. Hereinafter, the description of the same part as FIG. 1 is omitted. A hydrochloric acid aqueous solution 2 having a pH of 2 was added to both sides of the same container (reaction cell) 6 as in Example 1, and the ITO-TiO 2 electrode 4a and the ITO-Ag / TiO 2 electrode 4b were immersed in each aqueous solution 2. Furthermore, the circuit (FIG. 3) which connected both electrodes was comprised. Nitrogen and oxygen gas were bubbled through the ITO-TiO 2 electrode 4a and the ITO-Ag / TiO 2 electrode 4b for 1 hour while bubbling at a rate of 100 mL / min. After the supply of each gas was stopped and the cell was sealed, both electrodes were irradiated with light from a 480 W arc lamp. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. This on / off cycle was repeated seven times, and the change in the current flowing through the circuit was monitored. Generating a current density value in the first cycle is 26.7 μA / cm2, the current density value reaches elevated to 27.5μA / cm 2 up to the third cycle. In the subsequent cycles, the generated current decreased, and at the 7th cycle, it was 25.0 μA / cm 2 . Here, the area of each photocatalyst layer was 1.3 cm 2 .
さらに、図５のように回路を組み替え、可変抵抗を500kΩから0.3Ωに変化させながら電流-電圧特性を測定したところ、図7に示す曲線を得た。開放電圧は1.23Vと求められた（表1）。 Further, when the circuit was rearranged as shown in FIG. 5 and the current-voltage characteristics were measured while changing the variable resistance from 500 kΩ to 0.3Ω, the curve shown in FIG. 7 was obtained. The open circuit voltage was determined to be 1.23V (Table 1).
３．実施例３：生成酸素内部循環型光燃料電池
生成酸素内部循環型光燃料電池の概略については、図１で説明したとおりである。両側に石英窓が付いたパイレックス（登録商標）ガラス容器６の中央を仕切ったイオン交換膜であるプロトン伝導性高分子膜７の上方に気孔（6 mm×3 mm）を開けて反応セルとした。容器（反応セル）６の両側にpH2の塩酸水溶液を加え、ITO-TiO2電極４a及びITO-Ag/TiO2電極４bを、それぞれの水溶液２に浸した。アノード側の塩酸水溶液２の上にｎ−ヘキサンを加え有機相９とした。さらに両電極を結線した回路（図３）を構成した。ITO-TiO2電極４a及びITO-Ag/TiO2電極４bに、それぞれ窒素、酸素ガスを毎分100 mLの速度でバブルさせながら1時間流通させた。それぞれの気体の供給を止め、セルを密封した後、両電極に480Wアーク灯から光照射した。30分間光照射した後、光照射を30分間停止した。このon/offサイクルを7回繰り返し、回路に流れる電流の変化をモニターした。
1サイクル目の生成電流密度は53.6μA/cm2であった。生成電流密度はon/offサイクルを重ねるごとに徐々に減少し、7サイクル目では39.9 μA/cm2となった。 ここで光触媒層の面積はいずれも1.3 cm2であった。
3. Example 3: Generated oxygen internal circulation photofuel cell The outline of the generated oxygen internal circulation photofuel cell is as described in FIG. A pore (6 mm × 3 mm) was opened above the proton conductive polymer membrane 7, which is an ion exchange membrane partitioning the center of a Pyrex (registered trademark) glass container 6 with quartz windows on both sides to form a reaction cell. . A hydrochloric acid aqueous solution of pH 2 was added to both sides of the container (reaction cell) 6, and the ITO-TiO 2 electrode 4 a and the ITO-Ag / TiO 2 electrode 4 b were immersed in each aqueous solution 2. N-Hexane was added on the hydrochloric acid aqueous solution 2 on the anode side to obtain an organic phase 9. Furthermore, the circuit (FIG. 3) which connected both electrodes was comprised. Nitrogen and oxygen gas were bubbled through the ITO-TiO 2 electrode 4a and the ITO-Ag / TiO 2 electrode 4b for 1 hour while bubbling at a rate of 100 mL / min. After supply of each gas was stopped and the cell was sealed, both electrodes were irradiated with light from a 480 W arc lamp. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. This on / off cycle was repeated seven times, and the change in the current flowing through the circuit was monitored.
The generated current density in the first cycle was 53.6 μA / cm 2 . The generated current density gradually decreased with each on / off cycle, and reached 39.9 μA / cm 2 at the 7th cycle. Here, the area of each photocatalyst layer was 1.3 cm 2 .
さらに、図3のように回路を組み替え、可変抵抗を500 kΩから0.3 Ωに変化させながら電流-電圧特性を測定したところ、図7に示す曲線を得た。開放電圧は1.32Vと求められた（表1）。 Further, when the circuit was rearranged as shown in FIG. 3 and the current-voltage characteristics were measured while changing the variable resistance from 500 kΩ to 0.3 Ω, the curve shown in FIG. 7 was obtained. The open circuit voltage was determined to be 1.32V (Table 1).
図４、図７に実施例１、２、３の電流の時間変化及び生成電流密度−電圧測定結果の比較を示す。また、表1にI−V曲線から求めた電池性能を示した。 FIGS. 4 and 7 show a comparison of the time variation of the current and the generated current density-voltage measurement results of Examples 1, 2, and 3. FIG. Table 1 shows the battery performance determined from the IV curve.
酸素内部循環型光燃料電池（実施例３）にすることで、ガス閉鎖型光燃料電池（実施例２）よりも生成電流密度値が明らかに上昇したことが図４より分かった。さらに、実施例３での光燃料電池の出力は10.2μW/cm2となり、実施例２の2.4倍となった（表１）。両極に外部からガスを供給し続けるガス外部供給セル（実施例１）と比較しても87%の出力を得ており、遜色ない成績を得た。これらの結果から、酸素内部循環型光燃料電池の酸素循環の効果が実証され、完全に独立して発電する光燃料電池のフィージビリティが示された。 It was found from FIG. 4 that the generation current density value was clearly increased by using the oxygen internal circulation type photo fuel cell (Example 3) as compared with the gas closed type photo fuel cell (Example 2). Furthermore, the output of the photovoltaic fuel cell in Example 3 was 10.2 μW / cm 2 , which was 2.4 times that in Example 2 (Table 1). Even when compared with a gas external supply cell (Example 1) that continues to supply gas from the outside to both electrodes, an output of 87% was obtained, and an inferior result was obtained. From these results, the oxygen circulation effect of the oxygen internal circulation type photo fuel cell was demonstrated, and the feasibility of the photo fuel cell that generates electricity completely independently was shown.
本発明は、燃料電池として産業上の利用が可能である。 The present invention can be industrially used as a fuel cell.
１ 燃料電池
２ 酸水溶液
３a 窒素ガス
３b 酸素ガス
４a アノード電極
４b カソード電極
５a アノード側光触媒
５b カソード側光触媒
６ 収容部材
７ イオン交換膜
８ 外部回路
９ 酸素溶解層
DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Acid aqueous solution 3a Nitrogen gas 3b Oxygen gas 4a Anode electrode 4b Cathode electrode 5a Anode side photocatalyst 5b Cathode side photocatalyst 6 Housing member 7 Ion exchange membrane 8 External circuit 9 Oxygen dissolved layer
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