JP2017191649A - Composite type fuel battery system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite type fuel battery system which can organically combine a photo fuel battery and a direct methanol fuel battery and mutually utilize a product in one of the batteries as fuel for the other battery.SOLUTION: A composite type fuel battery system comprises a photovoltaic fuel battery 10 in which a first proton conductive polymer membrane 13 is sandwiched between a first anode 11 and a first cathode 12 each carrying a photocatalyst thereon to generate electric power through a photocatalytic reaction, a direct methanol fuel battery 20 in which a second proton conductive polymer membrane 23 is sandwiched between a second anode 21 and a second cathode 22 each carrying a catalyst thereon to generate electric power through a catalytic reaction, a methanol feed line L1 for feeding produced methanol when power generation is performed in the photovoltaic fuel battery 10, an oxygen feed line L2 for feeding oxygen, a water feed line L3 for feeding produced water when power generation is performed in the direct methanol fuel battery 20, and a carbon dioxide feed line L4 for feeding carbon dioxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite fuel cell system including a photo fuel cell and a direct methanol fuel cell.

  A fuel cell is a cell that generates power by a redox reaction of fuel, and has advantages in terms of high power generation efficiency and a small environmental load.

  A photofuel cell is a cell that uses a photocatalytic reaction to generate electricity using water as a fuel to generate oxygen, and at the same time reduce carbon dioxide or the like to generate methanol or the like (for example, Patent Document 1 described later). reference). The photovoltaic fuel cell has an advantage that it can simultaneously achieve reduction of carbon dioxide in the atmosphere and production of methanol or the like useful as fuel.

  A direct methanol fuel cell is a fuel cell that generates power by oxidizing methanol at a fuel electrode (see, for example, Patent Document 2 described later). In the direct methanol fuel cell, since the fuel is liquid methanol, the apparatus can be made compact, and the handling and safety of the fuel are excellent.

JP 2014-123554 A JP-A-2005-203161

  The photovoltaic fuel cell as described in Patent Document 1 has a problem that the amount of power generation is limited when sunlight is used as a light source. Moreover, the direct methanol fuel cell as described in Patent Document 2 has a problem of consuming methanol as a fuel and generating carbon dioxide, which is a greenhouse gas.

  The present invention has been made in view of the above, and provides a combined fuel cell system in which an optical fuel cell and a direct methanol fuel cell are organically combined, and one product can be mutually used as the other fuel. For the purpose.

  According to the present invention, a first proton conducting polymer membrane is sandwiched between a first anode and a first cathode each carrying a photocatalyst, and a first anode chamber is provided outside the first anode. A first cathode chamber is formed outside the cathode, and a second fuel-conducting polymer membrane is sandwiched between a photofuel cell that generates electric power by a photocatalytic reaction, and a second anode and a second cathode each carrying a catalyst. In addition, a second anode chamber is formed outside the second anode, and a second cathode chamber is formed outside the second cathode, and a direct methanol fuel cell that generates power by catalytic reaction, and when the photovoltaic fuel cell generates power, A methanol feed line that takes out the methanol produced in the first cathode chamber and feeds it to the second anode chamber, and is produced in the first anode chamber during power generation of the photovoltaic fuel cell. An oxygen supply line that extracts oxygen and supplies it to the second cathode chamber, and water that extracts water generated in the second cathode chamber and supplies it to the first anode chamber during power generation of the direct methanol fuel cell A hybrid fuel cell system comprising: a feed line; and a carbon dioxide feed line that takes out carbon dioxide generated in the second anode chamber and feeds it to the first cathode chamber during power generation of the direct methanol fuel cell. About.

  In addition, a methanol storage tank provided in the methanol supply line, an oxygen storage tank provided in the oxygen supply line, a water storage tank provided in the water supply line, and the carbon dioxide supply line It is preferable to provide a carbon dioxide storage tank.

  Moreover, it is preferable to provide a methanol replenishing means for replenishing the methanol storage tank from the outside and a water replenishing means for replenishing the water storage tank from the outside.

  The first storage amount detection means for detecting the methanol storage amount in the methanol storage tank, the second storage amount detection means for detecting the water storage amount in the water storage tank, and the detection amount of the first storage amount detection means are first. The methanol replenishing means is controlled to replenish methanol when it falls below one reference value, and / or water is replenished when the amount detected by the second storage amount detecting means falls below a second reference value. It is preferable to include a raw material replenishment control means for controlling the water replenishment means.

  ADVANTAGE OF THE INVENTION According to this invention, a composite fuel cell system which can combine an optical fuel cell and a direct methanol fuel cell organically, and can mutually utilize one product as the other fuel can be provided.

1 is a diagram showing an outline of a composite fuel cell system according to an embodiment of the present invention.

Hereinafter, an embodiment of a composite fuel cell system according to the present invention will be described with reference to the drawings. FIG. 1 is an overall schematic diagram of a composite fuel cell system 1 according to an embodiment of the present invention. The composite fuel cell system 1 includes an optical fuel cell 10 and a direct methanol fuel cell 20.
The composite fuel cell system 1 according to the present embodiment uses methanol W1 obtained from the photofuel cell 10 as a fuel for the direct methanol fuel cell 20, and water W3 obtained from the direct methanol fuel cell 20 as the fuel for the photofuel cell 10. To generate electricity.

  Specifically, as shown in FIG. 1, the composite fuel cell system 1 of the present embodiment includes a photo fuel cell 10, a direct methanol fuel cell 20, and methanol in which methanol W 1 generated by the photo fuel cell 10 circulates. A feed line L1, an oxygen feed line L2 through which the oxygen W2 generated by the photovoltaic fuel cell 10 flows, a water feed line L3 through which the water W3 generated by the direct methanol fuel cell 20 flows, and a direct methanol fuel A carbon dioxide supply line L4 through which the carbon dioxide W4 generated by the battery 20 circulates.

<Photo fuel cell>
The photofuel cell 10 includes a first anode 11, a first cathode 12, a first anode chamber 111, a first cathode chamber 121, a first proton conductive polymer membrane 13, and an external circuit 14. . The first anode 11 and the first cathode 12 each carry a photocatalyst. An oxygen supply line L2 and a water supply line L3 are connected to the first anode chamber 111. A methanol feed line L1 and a carbon dioxide feed line L4 are connected to the first cathode chamber 121.

The first anode 11 and the first cathode 12 are immersed in the aqueous solution in the first anode chamber 111 and the first cathode chamber 121, respectively. The first anode 11 and the first cathode 12 are electrically connected, and electrons generated in the first anode chamber 111 are supplied to the first cathode chamber 121 through the external circuit 14. Electric power is obtained by this movement of electrons.
The material of the first anode 11 and the first cathode 12 is not particularly limited as long as the above functions are not impaired. For example, carbon (C), indium tin oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide (TO And the like.

The first anode 11 and the first cathode 12 each carry a photocatalyst.
In the photocatalyst used in the present embodiment, by irradiating light having energy greater than the band gap, electrons in the valence band are excited to the conduction band, and the holes and excited electrons generated in the photocatalyst are respectively Functions as an oxidizing agent and a reducing agent.
The photocatalyst carried on the first anode 11 is a photooxidation catalyst that functions as an oxidizing agent that oxidizes water when irradiated with the light SL. Such a photo-oxidation catalyst is not particularly limited, and examples thereof include WO ₃ , TiO ₂ , SnO, and ZnO. Among them, it is preferable to use WO ₃ that can utilize sunlight and has strong oxidizing power because it has responsiveness to ultraviolet light and visible light.

The photocatalyst carried on the first cathode 12 is a photoreduction catalyst that functions as a reducing agent that reduces carbon dioxide when irradiated with light SL. As such an optical reduction catalyst is not particularly _{limited, TiO 2, SrTiO 2, Al} 2 O 3, WO 3 , and the like.

In the first anode chamber 111, as shown in the following formula (1), an oxidation reaction of water as a fuel is performed by the action of the photocatalyst carried on the first anode 11. Protons (H ⁺ ) generated by the oxidation reaction are in an excess state in the first anode chamber 111, and thus move to the first cathode chamber 121 through the first proton conductive polymer membrane 13. Similarly, electrons (e ⁻ ) generated by the oxidation reaction move from the first anode 11 to the first cathode 12 through the external circuit 14 and are supplied to the first cathode chamber 121.

Further, carbon dioxide (CO ₂ ) in the first cathode chamber 121 is reduced by the action of the photocatalyst carried on the first cathode 12 as shown by the following formula (2). This produces methanol. From the above, as shown in the following formula (3), methanol and oxygen are generated from water and carbon dioxide as a result of the oxidation-reduction reaction by the photocatalyst in the entire photofuel cell 10.
2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻ (1)
CO ₂ + 6H ⁺ + 6e ⁻ → CH ₃ OH + H ₂ O (2)
2H ₂ O + CO ₂ → CH ₃ OH + 3 / 2O ₂ (3)

The first anode chamber 111 and the first cathode chamber 121 are formed outside the first anode 11 and the first cathode 12, respectively, and contain an aqueous solution in which the first anode 11 and the first cathode 12 are immersed. An oxygen supply line L2 and a water supply line L3 are connected to the first anode chamber 111. A methanol feed line L1 and a carbon dioxide feed line L4 are connected to the first cathode chamber 121. The first anode chamber 111 and the first cathode chamber 121 are made of a light transmissive material so as not to prevent the light SL (ultraviolet light, visible light, etc.) from reaching the first anode 11 and the first cathode 12. Preferably it is formed. Such a material is not particularly limited, and examples thereof include glass such as quartz glass and light transmissive resin.
Further, since it is necessary to acquire oxygen generated in the first anode chamber 111 and supply carbon dioxide to the first cathode chamber 121 as described later, the first anode chamber 111 and the first cathode chamber 121 are constant. It is preferable to provide an airtight structure having the pressure resistance.

The aqueous solution in the first anode chamber 111 may be pure water, but is preferably an acid aqueous solution containing protons. By making the aqueous solution an acid aqueous solution, the reaction rate of the reaction involving protons increases.
Although it does not restrict | limit especially as an acid used for such an acid aqueous solution, For example, hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, carbonic acid etc. are mentioned.

The first proton conductive polymer membrane 13 is sandwiched between the first anode 11 and the first cathode 12, and partitions the first anode chamber 111 and the first cathode chamber 121. The proton conductive polymer membrane has high proton conductivity and has an insulating property to prevent a short circuit between the first anode 11 and the first cathode 12. In the present embodiment, oxygen is generated in the first anode chamber 111 and carbon dioxide is supplied in the first cathode chamber 121. Therefore, the first proton conductive polymer membrane 13 regulates the movement of these substances. To do.
Examples of such a proton conductive polymer membrane include a condensate of phenolsulfonic acid and formaldehyde, sulfonated polystyrene, trifluorostyrenesulfonic acid, fluorocarbonsulfonic acid, a mixture of fluorocarbonsulfonic acid and polyvinylidene fluoride, and the like. Is mentioned.

  As the first proton conductive polymer membrane 13, a commercially available product can be used. For example, “Nafion (registered trademark)” (manufactured by DuPont), “Flemion (registered trademark)” (manufactured by Asahi Glass Co., Ltd.), “ Aciplex (registered trademark) "(manufactured by Asahi Kasei Corporation) or the like can be used.

  The external circuit 14 is a circuit that electrically connects the first anode 11 and the first cathode 12. As described above, when electrons move from the first anode 11 to the first cathode 12 through the external circuit 14, electric power can be obtained in the external circuit 14.

<Direct methanol fuel cell>
The direct methanol fuel cell 20 includes a second anode 21, a second cathode 22, a second anode chamber 211, a second cathode chamber 221, a second proton conductive polymer membrane 23, and an external circuit 24. Prepare. A catalyst is supported on each of the second anode 21 and the second cathode 22. Note that a methanol feed line L1 and a carbon dioxide feed line L4 are connected to the second anode chamber 211. An oxygen supply line L2 and a water supply line L3 are connected to the second cathode chamber 221.

The second anode 21 and the second cathode 22 are immersed in the aqueous solution in the second anode chamber 211 and the second cathode chamber 221, respectively. The second anode 21 and the second cathode 22 are electrically connected, and electrons generated in the second anode chamber 211 move to the second cathode chamber 221 through the external circuit 24. Electric power is obtained by this movement of electrons.
The material of the second anode 21 and the second cathode 22 is not particularly limited as long as the function is not hindered. For example, carbon (C), indium tin oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide ( TO).

The second anode 21 and the second cathode 22 carry a catalyst metal that promotes the oxidation reaction of methanol and the reduction reaction of oxygen. Examples of such catalytic metals include simple metals such as Pt, Ru, Ir, Rh, Pd, and Os, and alloys thereof. In addition, although these catalyst metals may be carry | supported by the carbon electrode etc., you may use these catalyst metals as an electrode directly.
The second anode 21 and the second cathode 22 can basically have the same configuration. The second anode 21 is preferably used as a catalyst by supporting Pt—Ru alloy or both Pt particles and Ru particles in order to suppress poisoning caused by a small amount of CO.

In the second anode chamber 211, as shown in the following formula (4), an oxidation reaction of methanol as a fuel is performed by the action of the catalyst supported on the second anode 21. Protons (H ⁺ ) generated by the oxidation reaction are in an excess state in the second anode chamber 211, and thus move to the second cathode chamber 221 through the second proton conductive polymer membrane 23. Similarly, electrons (e ⁻ ) generated by the oxidation reaction move from the second anode 21 to the second cathode 22 through the external circuit 24 and are supplied to the second cathode chamber 221.

Further, oxygen in the second cathode chamber 221 is reduced by the action of the catalyst supported on the second cathode 22 as shown in the following formula (5). Thereby, water is generated. From the above, as shown in the following formula (6), water and carbon dioxide are generated from methanol and oxygen as a result of the oxidation-reduction reaction of the direct methanol fuel cell 20 as a whole.
CH ₃ OH + H ₂ O → CO ₂ + 6H ⁺ + 6e ⁻ (4)
O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O (5)
CH ₃ OH + 3 / 2O ₂ → 2H ₂ O + CO ₂ (6)

  Here, as shown in the above formulas (3) and (6), the fuel (reactant) in the photofuel cell 10 and the product in the direct methanol fuel cell 20 are theoretically exactly the same, including the amount of substances. It is. Further, the fuel (reactant) in the direct methanol fuel cell 20 and the product in the photovoltaic fuel cell 10 are theoretically exactly the same including the amount of substances. Therefore, the combined fuel cell system 1 theoretically eliminates the need for fuel supply by mutually using the products accompanying the power generation of the photovoltaic fuel cell 10 and the direct methanol fuel cell 20 as the respective fuels. It can function as a power generation system that does not exist.

The second anode chamber 211 and the second cathode chamber 221 are formed outside the second anode 21 and the second cathode 22, respectively, and contain an aqueous solution in which the second anode 21 and the second cathode 22 are immersed. A methanol feed line L1 and a carbon dioxide feed line L4 are connected to the second anode chamber 211. An oxygen supply line L2 and a water supply line L3 are connected to the second cathode chamber 221.
Since the second anode chamber 211 and the second cathode chamber 221 need to acquire carbon dioxide generated in the second anode chamber 211 and supply oxygen to the second cathode chamber 221, it has a certain pressure resistance. It is preferable to provide a sealing structure having

  The aqueous solution in the second anode chamber 211 may be an aqueous solution containing methanol. However, as shown in the above formula (4), in the second anode chamber 211, the reaction between methanol and water as reactants proceeds at a molar ratio of 1: 1. Therefore, the molar ratio of methanol and water in the aqueous solution in the second anode chamber 211 is preferably 1: 1 or close to that.

  The second proton conductive polymer membrane 23 is sandwiched between the second anode 21 and the second cathode 22 and partitions the second anode chamber 211 and the second cathode chamber 221. As the second proton conductive polymer membrane 23, the same material as the first proton conductive polymer membrane 13 can be used, but methanol in the second anode chamber 211 moves to the second cathode chamber 221. It is preferable that so-called crossover can be suppressed.

  The external circuit 24 is a circuit that electrically connects the second anode 21 and the second cathode 22. As described above, when the electrons move from the second anode 21 to the second cathode 22 through the external circuit 24, electric power can be obtained in the external circuit 24.

The methanol supply line L1 is a line through which the methanol W1 generated in the optical fuel cell 10 is directly supplied to the methanol fuel cell 20. The upstream end of the methanol feed line L 1 is connected to the first cathode chamber 121, and the downstream end is connected to the second anode chamber 211.
The methanol feed line L1 is provided with a methanol tank 15 as a methanol storage tank and a pump 16.

  The methanol tank 15 is a facility for storing methanol W1. The methanol tank 15 is connected with a methanol replenishment unit 151 as methanol replenishment means. A first storage amount sensor 152 is provided as first storage amount detection means for detecting the amount of methanol stored in the methanol tank 15.

The methanol replenishment unit 151 and the first storage amount sensor 152 are electrically connected to the control unit 17.
The control unit 17 is configured by a microprocessor (not shown) including a CPU and a memory. Based on the storage amount detection result of the first storage amount sensor 152, the control unit 17 controls the methanol replenishment unit 151 so that the methanol tank 15 is replenished with methanol when the detected amount is lower than the first reference value.

  The pump 16 is a device that sucks the methanol W1 and discharges it toward the second anode chamber 211 on the downstream side. The pump 16 is provided between the methanol tank 15 and the second anode chamber 211.

The oxygen supply line L <b> 2 is a line through which oxygen W <b> 2 generated in the photovoltaic fuel cell 10 is directly supplied to the methanol fuel cell 20. The upstream end of the oxygen supply line L2 is connected to the first anode chamber 111, and the downstream end is connected to the second cathode chamber 221.
The oxygen supply line L2 is provided with an oxygen tank 18 as an oxygen storage tank and a blower 19.
Note that the oxygen supply line L2 may be provided with an inlet for sucking air from outside air and using it as oxygen W2.

  The oxygen tank 18 is a facility for storing oxygen W2. The blower 19 is a device that sucks oxygen W2 and discharges it toward the second cathode chamber 221 on the downstream side. The blower 19 is provided between the oxygen tank 18 and the second cathode chamber 221.

The water supply line L3 is a line through which the water W3 generated in the direct methanol fuel cell 20 is supplied to the photovoltaic fuel cell 10. The upstream end of the water supply line L3 is connected to the second cathode chamber 221, and the downstream end is connected to the first anode chamber 111.
The water supply line L3 is provided with a water tank 25 as a water storage tank and a pump 26.

  The water tank 25 is a facility for storing the water W3. The water tank 25 is connected with a water replenishment unit 251 as water replenishment means, and is provided with a second storage amount sensor 252 as second storage amount detection means for detecting the water storage amount of the water tank 25.

The water replenishment unit 251 and the second storage amount sensor 252 are electrically connected to the control unit 27.
The control unit 27 includes a microprocessor (not shown) including a CPU and a memory. The control unit 27 controls the water replenishment unit 251 to replenish the water tank 25 with water when the detected amount is lower than the second reference value based on the storage amount detection result by the second storage amount sensor 252.

  The pump 26 is a device that sucks the water W3 and discharges it toward the first anode chamber 111 on the downstream side. The pump 26 is provided between the water tank 25 and the first anode chamber 111.

  The water W3 flowing through the water supply line L3 and the water stored in the water tank 25 and the water replenishing unit 251 may be pure water, but are not limited thereto, and may be an aqueous solution. An aqueous acid solution containing protons is preferred.

The carbon dioxide supply line L4 is a line through which the carbon dioxide W4 generated in the direct methanol fuel cell 20 is supplied to the optical fuel cell 10. The upstream end of the carbon dioxide supply line L4 is connected to the second anode chamber 211, and the downstream end is connected to the first cathode chamber 121.
The carbon dioxide supply line L4 is provided with a carbon dioxide tank 28 as a carbon dioxide storage tank and a blower 29.
The carbon dioxide supply line L4 may be provided with a suction port for sucking air from outside air and using it as carbon dioxide W4.

  The carbon dioxide tank 28 is a facility for storing carbon dioxide W4. The blower 29 is a device that sucks carbon dioxide W4 and discharges it toward the first cathode chamber 121 on the downstream side. The blower 29 is provided between the carbon dioxide tank 28 and the first cathode chamber 121.

  The composite fuel cell system 1 according to the present embodiment described above has the following effects.

  In the composite fuel cell system 1 of the present embodiment, a first proton conductive polymer membrane 13 is sandwiched between a first anode 11 and a first cathode 12 each carrying a photocatalyst, and the first anode 11 A first anode chamber 111 is formed on the outer side, and a first cathode chamber 121 is formed on the outer side of the first cathode 12. The photofuel cell 10 generates power by a photocatalytic reaction, and the second anode 21 and the second cathode each carrying a catalyst, respectively. The second proton conducting polymer membrane is sandwiched between the second anode chamber 21, the second anode chamber 211 is formed outside the second anode 21, and the second cathode chamber 221 is formed outside the second cathode 22. The direct methanol fuel cell 20 that generates electric power by the above and the methanol W1 generated in the first cathode chamber 121 during the power generation of the photofuel cell 10 are supplied to the second anode chamber 211 Methanol feed line L 1, oxygen feed line L 2 that feeds oxygen W 2 generated in the first anode chamber 111 to the second cathode chamber 221, and direct power generation in the methanol fuel cell 20 in the second cathode chamber 221. A water supply line L3 that supplies the generated water W3 to the first anode chamber 111 and a carbon dioxide supply line L4 that takes out the carbon dioxide W4 generated in the second anode chamber 211 and supplies it to the first cathode chamber 121. And comprising.

  Therefore, the methanol generated in the photofuel cell 10 can be used as a fuel in the direct methanol fuel cell 20, and at the same time, the water generated in the direct methanol fuel cell 20 can be used as a fuel in the photofuel cell 10. Therefore, it is possible to provide the composite fuel cell system 1 in which one product can be mutually used as the other fuel.

  Further, a methanol tank 15 is provided in the methanol feed line L1, an oxygen tank 18 is provided in the oxygen feed line L2, a water tank 25 is provided in the water feed line L3, and carbon dioxide is provided in the carbon dioxide feed line L4. A tank 28 is provided.

  Therefore, it is possible to store methanol and oxygen generated by the photofuel cell 10 and water and carbon dioxide generated directly by the methanol fuel cell 20, respectively. Thus, for example, power is generated by the photovoltaic fuel cell 10 while sunlight can be used, the generated methanol and oxygen are stored, and power is directly generated by the methanol fuel cell 20 while sunlight is not used. Operation such as storing water and carbon dioxide becomes possible. Therefore, stable power generation is possible by the composite fuel cell system 1.

  The composite fuel cell system 1 according to the present embodiment includes a methanol replenishment unit 151 that replenishes methanol to the methanol tank 15 from the outside, and a water replenishment unit 251 that replenishes the water tank 25 from the outside.

  Therefore, even when the methanol as the fuel in the direct methanol fuel cell 20 runs out, it is possible to generate power directly in the methanol fuel cell 20 by replenishing methanol from the outside. Similarly, even when the water that is the fuel in the photofuel cell 10 is exhausted, it is possible to generate power in the photofuel cell 10 by replenishing water from the outside. As described above, the composite fuel cell system 1 can continuously and stably generate power.

  The composite fuel cell system 1 of the present embodiment includes a first storage amount sensor 152 that detects the amount of methanol stored in the methanol tank 15 and methanol when the detection amount in the first storage amount sensor 152 is lower than the first reference value. The control unit 17 that controls the methanol replenishment unit 151 to replenish the water, the second storage amount sensor 252 that detects the amount of water stored in the water tank 25, and the detection amount in the second storage amount sensor 252 has the second reference value. And a control unit 27 that controls the water replenishment unit 251 so as to replenish water when the ratio is lower.

  Therefore, when the storage amounts of the methanol tank 15 and the water tank 25 become below a certain level, the fuel methanol and water are automatically replenished. Therefore, management of the composite fuel cell system 1 is facilitated, and power generation can be performed stably and continuously.

  The preferred embodiment of the composite fuel cell system of the present invention has been described above, but the present invention is not limited to the above-described embodiment, and can be modified as appropriate.

  For example, in the present embodiment, the oxygen supply line L2 and the carbon dioxide supply line L4 are provided with only a tank and a blower, respectively, but are not limited thereto. That is, the oxygen supply line L2 and the carbon dioxide supply line L4 may be provided with external replenishment means such as an oxygen replenishment unit and a carbon dioxide replenishment unit. The replenishing means may use oxygen or carbon dioxide in the atmosphere.

  Moreover, in this embodiment, the control part 17 which controls the methanol replenishment part 151 and the control part 27 which controls the water replenishment part 251 are provided separately, but it is not limited to this. It is good also as a structure which controls both the methanol replenishment part 151 and the water replenishment part 251 with a single control part.

DESCRIPTION OF SYMBOLS 1 Composite type fuel cell system 10 Photofuel cell 11 1st anode 111 1st anode chamber 12 1st cathode 121 1st cathode chamber 13 1st proton conductive polymer membrane 15 Methanol tank (methanol storage tank)
151 Methanol replenishment section (methanol replenishment means)
152 1st storage amount sensor (1st storage amount detection means)
17 Control unit (raw material replenishment control means)
18 Oxygen tank (oxygen storage tank)
20 Direct Methanol Fuel Cell 21 Second Anode 211 Second Anode Chamber 22 Second Cathode 221 Second Cathode Chamber 23 Second Proton Conducting Polymer Membrane 25 Water Tank (Water Reservoir)
251 Water replenishment section (water replenishment means)
252 Second storage amount sensor (second storage amount detection means)
27 Control unit (raw material replenishment control means)
28 Carbon dioxide tank (carbon dioxide storage tank)
L1 Methanol supply line L2 Oxygen supply line L3 Water supply line L4 Carbon dioxide supply line

Claims (4)

A first proton-conducting polymer membrane is sandwiched between a first anode and a first cathode, each carrying a photocatalyst, and a first anode chamber is located outside the first anode, and a first anode chamber is located outside the first cathode. A photo-fuel cell in which a first cathode chamber is formed and generates power by a photocatalytic reaction;
A second proton conducting polymer membrane is sandwiched between a second anode and a second cathode each carrying a catalyst, and a second anode chamber is disposed outside the second anode, and the second anode chamber is disposed outside the second cathode. A direct methanol fuel cell in which a second cathode chamber is formed and generates electricity by catalytic reaction;
A methanol feed line for taking out methanol generated in the first cathode chamber and feeding it to the second anode chamber during power generation of the photofuel cell;
An oxygen supply line that takes out the oxygen generated in the first anode chamber and supplies it to the second cathode chamber during power generation of the photovoltaic fuel cell;
A water supply line for taking out the water generated in the second cathode chamber and feeding it to the first anode chamber during power generation of the direct methanol fuel cell;
And a carbon dioxide feed line for taking out carbon dioxide produced in the second anode chamber and feeding it to the first cathode chamber during power generation of the direct methanol fuel cell. A methanol storage tank provided in the methanol supply line;
An oxygen storage tank provided in the oxygen supply line;
A water storage tank provided in the water supply line;
The composite fuel cell system according to claim 1, further comprising a carbon dioxide storage tank provided in the carbon dioxide supply line. Methanol replenishing means for replenishing methanol from the outside to the methanol storage tank;
The combined fuel cell system according to claim 2, further comprising water replenishing means for replenishing the water storage tank from the outside. First storage amount detection means for detecting the methanol storage amount of the methanol storage tank;
Second storage amount detection means for detecting the amount of water stored in the water storage tank;
When the detection amount of the first storage amount detection means is lower than the first reference value, the methanol replenishment means is controlled to replenish methanol, and / or the detection amount of the second storage amount detection means is the first amount. 4. The composite fuel cell system according to claim 3, further comprising: a raw material replenishment control unit that controls the water replenishment unit so as to replenish water when the value is less than 2 reference values.

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