WO2012001839A1 - 直接酸化型燃料電池システム - Google Patents
直接酸化型燃料電池システム Download PDFInfo
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- WO2012001839A1 WO2012001839A1 PCT/JP2011/001111 JP2011001111W WO2012001839A1 WO 2012001839 A1 WO2012001839 A1 WO 2012001839A1 JP 2011001111 W JP2011001111 W JP 2011001111W WO 2012001839 A1 WO2012001839 A1 WO 2012001839A1
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- Prior art keywords
- fuel
- water
- oxidant
- drainage
- fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- 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
Definitions
- the present invention relates to a direct oxidation fuel cell system including a direct methanol fuel cell, and more particularly to an improvement in a gas-liquid separation mechanism that separates moisture from a fluid generated at the cathode of the fuel cell during power generation.
- Fuel cells are being put into practical use as in-vehicle power supplies, household cogeneration system power supplies, and the like.
- a fuel cell as a power source for portable small electronic devices such as notebook personal computers, cellular phones, and personal digital assistants (PDAs) has been studied. Since the fuel cell can generate power continuously by replenishing fuel, it is expected that the convenience of the portable electronic device can be further improved.
- DOFC direct oxidation fuel cell
- DMFC direct methanol fuel cell
- the fuel cell includes a stack in which a plurality of cells are connected in series.
- Each cell includes a membrane-electrode assembly including an electrolyte membrane and an anode and a cathode disposed on both sides of the electrolyte membrane, an anode-side separator in contact with the anode, and a cathode-side separator in contact with the cathode.
- the anode side separator has a fuel channel for supplying liquid fuel to the anode
- the cathode side separator has an oxidant channel for supplying oxidant to the cathode.
- the liquid fuel and the oxidant are supplied to the fuel cell by a supply device such as a pump.
- methanol and water react to produce carbon dioxide.
- Fuel drainage containing carbon dioxide and unreacted fuel is sent to a drainage tank.
- the cathode produces more water than is consumed at the anode. Part of the fluid containing water and unreacted oxygen is sent to the drainage tank.
- Patent Document 1 proposes that a filter for purifying the fluid discharged to the outside is provided in a pipe through which the fluid passes.
- Patent Document 2 proposes that the water-absorbing sheet absorb water vapor discharged from the cathode so as not to affect surrounding equipment.
- Patent Document 2 even if it is intended to absorb water vapor in the water absorbent sheet, depending on the positional relationship between the flow path of the fluid and the water absorbent sheet, there is a high possibility that the condensed water is accumulated locally, Eventually, it will block the passage of fluid. Moreover, it is difficult to control the amount of water vapor released to the outside simply by disposing the water absorbing sheet so as to be adjacent to the fuel cell. Therefore, it becomes difficult to control the amount of water collected in the drainage tank.
- the direct oxidation fuel cell system of the present invention includes at least one cell, a fuel inlet for introducing liquid fuel, a fuel outlet for discharging fuel drainage, an oxidant inlet for introducing oxidant, and an unconsumed oxidant. And an oxidant outlet that discharges a fluid containing generated water, a fuel supply unit that supplies the liquid fuel to a fuel inlet, an oxidant supply unit that supplies the oxidant to an oxidant inlet, A drainage tank that contains the fuel drainage and part of the generated water, a fuel discharge path that guides the fuel drainage to the drainage tank, and a gas that separates part of the generated water from the fluid and discharges the remainder to the outside.
- the gas-liquid separation mechanism includes an exhaust port that communicates the oxidant outlet and the outside, a porous filter that closes the exhaust port, and a water-absorbing material that partially covers the surface of the porous filter on the oxidant outlet side. And having.
- FIG. 1 is a schematic configuration diagram of a direct oxidation fuel cell system according to an embodiment of the present invention. It is sectional drawing perpendicular
- FIG. 6 is a cross-sectional view of the drainage tank taken along line VIb-VIb.
- the direct oxidation fuel cell system of the present invention will be described with reference to FIG.
- the fuel cell 2 included in the fuel cell system 1 includes a main body 2a, a fuel inlet 2b for introducing liquid fuel, a fuel outlet 2c for discharging fuel drainage, an oxidant inlet 2d for introducing oxidant, and no consumption. And an oxidant outlet 2e for discharging a fluid containing the oxidant and generated water.
- the main body 2a generally includes a stack in which two or more cells are stacked so as to be electrically connected in series.
- the cell 10 is a direct methanol fuel cell, and includes a polymer electrolyte membrane 12 and an anode 14 and a cathode 16 disposed so as to sandwich the polymer electrolyte membrane 12 therebetween.
- the polymer electrolyte membrane 12 has hydrogen ion conductivity.
- Methanol as a fuel is supplied to the anode 14.
- Air that is an oxidant is supplied to the cathode 16.
- an anode side separator 26 is stacked on the anode 14, and an end plate 46 ⁇ / b> A is disposed further on the anode side separator 26.
- a cathode side separator 36 is laminated on the cathode 16 (downward in the figure), and an end plate 46B is disposed further above the cathode side separator 36.
- the end plates 46A and 46B are not provided for each cell, but are arranged one at each end in the stacking direction of the cell stack.
- Each end plate functions as a current collecting plate that relays the power sent to the output terminals 2x and 2y of the fuel cell, and the power is sent to an external load (not shown) and the storage battery 103 via the DC / DC converter 102.
- a gasket 42 is disposed between the anode side separator 26 and the polymer electrolyte membrane 12 so as to surround the anode 14, and between the cathode side separator 36 and the polymer electrolyte membrane 12, so as to surround the cathode 16.
- a gasket 44 is disposed. Gaskets 42 and 44 prevent fuel and oxidant from leaking out of anode 14 and cathode 16, respectively.
- the two end plates 46A and 46B are fastened to each other so as to pressurize each separator and MEA (Membrane-Electrode-Assembly: membrane-electrode assembly) with bolts and springs (not shown) to constitute the cell 10. .
- MEA Membrane-Electrode-Assembly: membrane-electrode assembly
- the anode 14 includes an anode catalyst layer 18 and an anode diffusion layer 20.
- the anode catalyst layer 18 is in contact with the polymer electrolyte membrane 12.
- the anode diffusion layer 20 includes an anode porous substrate 24 that has been subjected to a water-repellent treatment, and an anode water-repellent layer 22 that is formed on the surface and is made of a highly water-repellent material.
- the anode water repellent layer 22 and the anode porous substrate 24 are laminated in this order on the surface of the anode catalyst layer 18 opposite to the surface in contact with the polymer electrolyte membrane 12.
- the cathode 16 includes a cathode catalyst layer 28 and a cathode diffusion layer 30.
- the cathode catalyst layer 28 is in contact with the surface of the polymer electrolyte membrane 12 opposite to the surface with which the anode catalyst layer 18 is in contact.
- the cathode diffusion layer 30 includes a cathode porous substrate 34 that has been subjected to water repellent treatment, and a cathode water repellent layer 32 that is formed on the surface thereof and is made of a highly water repellent material.
- the cathode water repellent layer 32 and the cathode porous substrate 34 are laminated in this order on the surface of the cathode catalyst layer 28 opposite to the surface in contact with the polymer electrolyte membrane 12.
- a laminate composed of the polymer electrolyte membrane 12, the anode catalyst layer 18 and the cathode catalyst layer 28 is responsible for power generation of the fuel cell, and is called CCM (Catalyst Coated Membrane).
- the MEA is a laminate composed of CCM, the anode diffusion layer 20 and the cathode diffusion layer 30.
- the anode diffusion layer 20 and the cathode diffusion layer 30 are responsible for the uniform dispersion of the fuel and the oxidant supplied to the anode 14 and the cathode 16 and the smooth discharge of the water and carbon dioxide as products.
- the anode-side separator 26 has a fuel flow path 38 for supplying fuel to the anode 14 on the contact surface with the anode porous substrate 24.
- the fuel flow path 38 is formed of, for example, a recess or groove formed on the contact surface and opening toward the anode porous substrate 24.
- the fuel flow path communicates with the fuel inlet 2b and the fuel outlet 2c of the fuel cell body 2a.
- the cathode side separator 36 has an oxidant channel 40 for supplying an oxidant (air) to the cathode 16 on the contact surface with the cathode porous substrate 34.
- the oxidant channel 40 is also formed of, for example, a recess or groove formed on the contact surface and opening toward the cathode porous substrate 34.
- the oxidant flow path communicates with the oxidant inlet 2d and the oxidant outlet 2e of the fuel cell main body 2a.
- the fuel cell system 1 further includes a fuel pump 3 that constitutes a fuel supply unit that supplies liquid fuel to the fuel inlet, and an air pump 4 that constitutes an oxidant supply unit that supplies oxidant to the oxidant inlet. .
- the outputs of the fuel pump 3 and the air pump 4 are normally controlled by a predetermined control device 5.
- a microcomputer or the like provided with a calculation unit 5a is used.
- the fuel pump 3 communicates with the fuel tank 6 and the drainage tank 7 containing the high-concentration supplementary fuel 6a.
- the supplementary fuel merges with the fuel drainage liquid 6b at the junction 8 provided upstream or downstream of the fuel pump.
- the liquid fuel 6c whose concentration is adjusted by the supplementary fuel 6a is guided to the fuel inlet 2b of the fuel cell. That is, the fuel pump 3 serves as a circulation pump that circulates the fuel drainage from the drainage tank 7 to the fuel inlet.
- the merging section 8 may have a mixing tank for temporarily retaining and mixing the replenished fuel 6a and the fuel drainage liquid 6b.
- the fuel supply unit includes at least a fuel pump (first fuel pump) 3, but at least a part that controls the fuel pump 3 in the control device 5, a fuel tank 6, and a joining unit 8 that joins supplementary fuel with the fuel drainage.
- the fuel supply unit may separately include a circulation pump (second fuel pump) that guides the fuel drainage liquid 6 b from the drainage tank 7 to the junction 8.
- the fuel supply unit may further include a supplementary fuel pump (third fuel pump) for controlling the amount of supplementary fuel 6 a guided to the junction 8 between the fuel tank 6 and the junction 8.
- the outputs of the second and third fuel pumps may be controlled by the control device 5 described above.
- the liquid fuel 6c is introduced into the fuel flow path from the fuel inlet 2b, passes through the flow path while consuming fuel, and is finally discharged from the fuel outlet 2c as a fuel drainage containing carbon dioxide.
- the fuel concentration in the fuel effluent has decreased, it contains unreacted fuel, so that it is reused after carbon dioxide is separated.
- the fuel drainage liquid is collected in the drainage tank 7 through the fuel discharge passage 9 that connects the fuel outlet 2 c and the drainage tank 7.
- the carbon dioxide separation method is not particularly limited.
- a window is provided in the drainage tank 7, and the window can be discharged to the outside by closing the window with a gas-liquid separation membrane that allows carbon dioxide to pass therethrough.
- a pair of electrodes 7a is preferably provided inside the drainage tank 7 as a sensor for measuring the amount of liquid. By doing in this way, a liquid quantity can be monitored with the electrostatic capacitance between the electrodes 7a.
- a temperature control device 7b for controlling the liquid temperature inside or outside the drainage tank 7.
- the air pump 4 plays a role of taking in air from the outside and guiding it to the oxidant inlet 2d of the fuel cell as an oxidant.
- the oxidant supply unit includes at least the air pump 4, a portion that controls the air pump 4 in the control device 5 may be interpreted as a part of the oxidant supply unit.
- Air is introduced into the oxidant flow path from the oxidant inlet 2d, passes through the flow path while consuming oxygen, and is finally discharged from the oxidant outlet 2e as a fluid containing water vapor (product water). .
- the discharged fluid is guided to the gas-liquid separation mechanism 100 by the pressure from the air pump 4.
- the gas-liquid separation mechanism 100 separates a part of the generated water from the discharged fluid and discharges the remaining part to the outside.
- methanol used as the fuel
- 3 mol of water is generated at the cathode. Therefore, in theory, the amount of water in the system can be maintained substantially constant by recovering the amount of water corresponding to one mole of the generated water.
- the remaining 2 moles of water are discharged to the outside through the gas-liquid separation mechanism 100.
- the separated produced water passes through the produced water drainage channel 101 and is collected in the drainage tank 7.
- the generated water drainage channel 101 communicates the gas-liquid separation mechanism 100 and the drainage tank 7.
- the gas-liquid separation mechanism 100 partially covers the exhaust port 104 communicating the oxidant outlet 2e and the outside, the porous filter 105 closing the exhaust port 104, and the surface of the porous filter 105 on the oxidant outlet side. And a water absorbing material 106.
- the exhaust port 104 communicating the oxidant outlet 2e with the outside is an opening for releasing air containing unconsumed oxidant (unreacted oxygen) to the outside.
- the exhaust port 104 is provided so as to always pass therethrough.
- the exhaust port 104 may be provided in a member that regulates the oxidant outlet 2e of the fuel cell, or may be provided in another member adjacent to such a member.
- the gas-liquid separation mechanism 100 includes a casing 107 and a filter unit (see FIG. 4), and the filter unit includes a porous filter 105 and a water absorbing material 106.
- the casing 107 has substantially the same shape as the oxidant outlet 2e, and includes a first opening 107a that is directly connected to the oxidant outlet, and a second opening (exhaust port) 104 that is provided to face the first opening. .
- the second opening 104 is closed by the porous filter 105, but the water absorbing material 106 is accommodated in the housing 107 so as to partially cover the porous filter 105. Therefore, the fluid discharged from the cathode passes through a region (hereinafter referred to as a first region) S1 that is mainly not covered with the water-absorbing material 106 of the porous filter 105 and is discharged to the outside.
- the fluid discharged from the cathode contains moisture
- the fluid aggregates in the pores of the porous filter 105 and the moisture is accumulated in the porous filter 105.
- This moisture moves to the water-absorbing material 106 by, for example, capillary action through the region (second region) S2 covered with the water-absorbing material 106 of the porous filter 105.
- the first region S1 since air is always in circulation, the moisture is easily volatilized. Therefore, moisture is difficult to accumulate in the first region S1, and an increase in pressure loss of the air pump is suppressed.
- the moisture distribution is the smallest in the first region S 1 of the porous filter 105 and the largest in the water-absorbing material 106.
- an increase in pressure loss when the oxidant is sent to the cathode is suppressed, and furthermore, an appropriate amount of water vapor is released to the outside and a necessary amount of moisture is discharged. It can be collected in the drainage tank 107.
- the second opening 104 is blocked by the porous filter 105, dust can be prevented from entering the vicinity of the exhaust port.
- the area of the second opening 104 is preferably smaller than the area of the first opening 107a.
- the water absorbing material 106 is preferably accommodated in the housing 107 so as not to enter the cylindrical space 109 between the first opening 107 a and the second opening 104. By doing so, it is possible to prevent air from passing through the second region S2 and to prevent excessive volatilization of moisture. In addition, since a sufficient air flow path can be secured, an increase in pressure loss can be easily suppressed.
- the generated water discharge path 101 may be provided with a suction pump 111 that sucks water held by the water absorbent material 106.
- a suction pump 111 that sucks water held by the water absorbent material 106.
- the suction pump 111 includes a nozzle 112 inserted into the water-absorbing material 106, and water is sent from the nozzle 112 to the suction pump.
- porous filter 105 a porous material capable of circulating air is used.
- a porous material is preferably a carbon sheet such as a carbon porous body, carbon paper, or carbon nonwoven fabric.
- the porous material 105 preferably has hydrophilicity.
- a carbon sheet imparted with moderate hydrophilicity is suitable as a porous filter. Since the carbon sheet imparted with hydrophilicity is easy to take up moisture and release moisture, moisture is hardly accumulated in the porous filter.
- the carbon porous body can be obtained by forming a mixture of carbon powder and a binder into a sheet shape.
- the amount of the binder is appropriately adjusted so that the formed sheet has an appropriate pore volume.
- the powder physical properties such as the particle size distribution of the carbon powder are also appropriately selected according to the desired average pore diameter and pore volume.
- Commercially available carbon paper, carbon non-woven fabric, etc. can be used.
- the porous filter 105 preferably has pores having an average pore diameter of 0.4 to 1.2 mm, more preferably 0.6 to 1.0 mm.
- an average pore diameter can be measured by using a palm porometer, for example.
- the method for imparting hydrophilicity to the carbon sheet is not particularly limited, and examples thereof include a method such as argon plasma treatment.
- the degree of hydrophilicity imparted is preferably such that the contact angle between the carbon sheet and water is 10 ° or less.
- the contact angle can be measured by a method such as the ⁇ / 2 method.
- the water absorbent material 106 should not cover the entire surface of the porous filter 105 on the oxidant outlet side (water absorbent material side). is important.
- the ratio of the surface on the oxidant outlet side of the porous filter 105 covered with the water absorbing material 106 (that is, the ratio of the area of the second region) is preferably 60 to 90%. If the area ratio of the second region S ⁇ b> 2 becomes too small, it takes time for water to move from the porous filter 105 to the water-absorbing material 106, and water tends to accumulate in the porous filter 105. As a result, the effect of suppressing an increase in pressure loss when sending the oxidant to the cathode is reduced. On the other hand, since the area of 1st area
- the thickness of the porous filter 105 varies depending on the kind of the porous material constituting it, but for example, when a carbon sheet is used, it is preferably 3 to 6 mm, more preferably 4 to 5 mm. If the porous filter 105 is too thick, the effect of suppressing the pressure loss when the oxidant is fed to the cathode is reduced. If the porous filter 105 is too thin, the strength of the first region S1 that is not particularly covered with the water-absorbing material is increased. Get smaller.
- the water-absorbing material 106 is desired to be a material that is easier to absorb and retain moisture than the porous filter 105.
- a porous material having such a characteristic that when immersed in a liquid, the liquid is absorbed in a form that replaces the air in the pores and is easily released by an external force, is preferable.
- a material that does not increase the apparent volume even when it absorbs liquid is preferable, and a material that increases the volume increase rate to 5% or less even when the liquid is contained as much as possible is preferable.
- natural sponge, sponge made of synthetic resin, pulp, polypropylene / polyethylene composite fiber, etc. can be preferably used.
- the thickness of the water-absorbing material 106 is not particularly limited, but it is desired that a predetermined amount of water can be accumulated while reducing the size of the filter portion. It is preferably 4 to 8 mm.
- the drainage tank 7 includes, for example, a container 113 having a window portion 113a at the top, and is configured to close the window portion 113a with a gas-liquid separation membrane 114 that allows carbon dioxide to pass therethrough.
- a water-repellent material is preferably used for the gas-liquid separation membrane 114.
- a material in which particles of polytetrafluoroethylene are formed into a sheet shape by welding is used. Since such a material allows water vapor to pass therethrough, when the amount of liquid in the drainage tank 7 becomes excessive, when the drainage tank 107 is heated, the moisture is converted into water vapor through the gas-liquid separation membrane. Can be released to the outside.
- the drainage tank 7 is preferably provided with a pair of electrodes 7a and a temperature sensor 115 as a liquid amount sensor.
- the fuel cell system of the present invention has high affinity with water and can be applied to all direct oxidation fuel cells that use liquid fuel at room temperature.
- fuel include hydrocarbon liquid fuels such as methanol, ethanol, dimethyl ether, formic acid, and ethylene glycol.
- the concentration of the aqueous methanol solution sent to the anode of the fuel cell is preferably 1 mol / L to 8 mol / L.
- a more preferable concentration of the methanol aqueous solution is 3 mol / L to 5 mol / L.
- MCO methanol crossover
- Example 1 An anode catalyst support including anode catalyst particles and a conductive support that supports the anode catalyst particles was prepared.
- anode catalyst particles platinum-ruthenium alloy (atomic ratio 1: 1) (average particle size: 5 nm) was used.
- carbon particles having an average primary particle size of 30 nm were used.
- the weight of the platinum-ruthenium alloy in the total weight of the platinum-ruthenium alloy and the carbon particles was 80% by weight.
- a cathode catalyst support including cathode catalyst particles and a conductive carrier supporting the particles was prepared. Platinum (average particle size: 3 nm) was used as the cathode catalyst particles. As the carrier, carbon particles having an average primary particle size of 30 nm were used. The weight of platinum in the total weight of platinum and carbon particles was 80% by weight.
- the polymer electrolyte membrane includes a 50 ⁇ m-thick fluoropolymer membrane (a film based on perfluorocarbon sulfonic acid / tetrafluoroethylene copolymer (H + type), trade name “Nafion (registered trademark) 112”, DuPont) was used.
- CCM production Formation of anode
- Dispersion containing 10 g of anode catalyst carrier and perfluorocarbonsulfonic acid / tetrafluoroethylene copolymer (H + type) (Nafion dispersion, “Nafion (registered trademark) 5 wt% solution”, manufactured by DuPont) 70 g of was mixed with an appropriate amount of water by stirring with a stirrer. Thereafter, the obtained mixture was degassed to obtain an anode catalyst layer forming ink.
- the anode catalyst layer-forming ink was applied by spraying on one surface of the polymer electrolyte membrane by a spray method using an air brush to form a 40 ⁇ 90 mm rectangular anode catalyst layer.
- the dimensions of the anode catalyst layer were adjusted by masking.
- the ink for forming the anode catalyst layer was sprayed, the polymer electrolyte membrane was adsorbed and fixed to a metal plate whose surface temperature was adjusted by a heater under reduced pressure.
- the ink for forming the anode catalyst layer was gradually dried during application.
- the thickness of the anode catalyst layer was 61 ⁇ m.
- the amount of Pt—Ru per unit area was 3 mg / cm 2 .
- the cathode catalyst layer forming ink was applied to the surface of the polymer electrolyte membrane opposite to the surface on which the anode catalyst layer was formed in the same manner as the anode catalyst layer was formed. As a result, a rectangular cathode catalyst layer of 40 ⁇ 90 mm was formed on the polymer electrolyte membrane. The amount of Pt per unit area contained in the formed cathode catalyst layer was 1 mg / cm 2 .
- the anode catalyst layer and the cathode catalyst layer were arranged so that their centers (intersections of rectangular diagonal lines) were located on one straight line parallel to the thickness direction of the polymer electrolyte membrane.
- a CCM was produced as described above.
- PTFE was used in the same manner as the porous anode substrate except that carbon cloth (trade name “AvCarb TM 1071HCB”, manufactured by Ballard Material Products) was used instead of carbon paper subjected to water repellent treatment.
- a cathode porous substrate having a content of 10% by weight was prepared.
- anode porous substrate coated with the water repellent layer forming ink was baked at 270 ° C. for 2 hours in an electric furnace to remove the surfactant.
- an anode water-repellent layer was formed on the anode porous substrate to obtain an anode diffusion layer.
- cathode water repellent layer (Preparation of cathode water repellent layer) A cathode water repellent layer was formed on one surface of the cathode porous substrate in the same manner as the anode water repellent layer to obtain a cathode diffusion layer.
- the anode diffusion layer and the cathode diffusion layer were both formed into a 40 ⁇ 90 mm rectangle using a punching die.
- the anode diffusion layer and the CCM were laminated so that the anode water repellent layer and the anode catalyst layer were in contact with each other. Further, the cathode diffusion layer and the CCM were laminated so that the cathode water repellent layer and the cathode catalyst layer were in contact with each other.
- the obtained laminated body was pressurized at a pressure of 5 MPa for 1 minute by a hot press apparatus in which the temperature was set to 125 ° C.
- the anode catalyst layer and the anode diffusion layer were joined together, and the cathode catalyst layer and the cathode diffusion layer were joined.
- a membrane-electrode assembly comprising an anode, a polymer electrolyte membrane, and a cathode was obtained.
- a rectangular resin-impregnated graphite plate having a thickness of 1.5 mm and a size of 50 ⁇ 120 mm was prepared.
- the surface of the graphite plate was cut to form a fuel flow path for supplying an aqueous methanol solution to the anode.
- An inlet portion (fuel inlet) of the fuel flow path is disposed on one of the short side end portions of the separator.
- an outlet part (fuel outlet) of the fuel flow path was arranged.
- a rectangular resin-impregnated graphite plate having a thickness of 2 mm and a size of 50 ⁇ 120 mm was prepared as a material for the cathode side separator.
- the surface was cut to form an air flow path for supplying air as an oxidant to the cathode.
- An inlet portion (oxidant inlet) of the air flow path is disposed on one of the short side end portions of the separator.
- an outlet portion (oxidant outlet) of the air flow path was disposed. In this way, a cathode side separator was produced.
- the cross-sectional shapes of the grooves constituting the fuel flow path and the air flow path were 1 mm wide and 0.5 mm deep, respectively.
- the fuel flow path and the air flow path are serpentine types that can supply fuel and air uniformly to the respective parts of the anode diffusion layer and the cathode diffusion layer.
- the anode separator was laminated with MEA so that the fuel flow path was in contact with the anode diffusion layer.
- the cathode side separator was laminated with MEA so that the air flow path was in contact with the cathode diffusion layer.
- a carbon sheet having a thickness of 4 mm and an average pore diameter of 0.6 mm and subjected to a hydrophilic treatment was cut into a shape of 10 mm ⁇ 35 mm to obtain a porous filter.
- the contact angle between the porous filter and water was 10 °.
- a container-like housing made of polypropylene resin having an opening (first opening) having a shape corresponding to the porous filter was obtained by molding.
- a second opening (exhaust port) of 3 ⁇ 35 mm was formed at a position biased toward one long side of the bottom of the casing. Then, the porous filter was fitted into the casing so as to close the second opening from the inside of the casing.
- a natural sponge sheet (water-absorbing material) having a thickness of 4 mm was cut into a shape of 7 mm ⁇ 35 mm, fitted in a position not overlapping the second opening in the housing, and brought into contact with the porous filter.
- the filter part was formed in the housing.
- the surface of the water-absorbing material on the first opening side was flush with the end of the casing that regulates the first opening.
- the area ratios of the region not covered with the water-absorbing material (first region) and the region covered with the water-absorbing material (second region) of the porous filter were 30% and 70%, respectively.
- a small hole with a diameter of 2 mm was formed on the side of the housing so as to face the sponge.
- a cylindrical nozzle was inserted into the sponge from this small hole, and then the gap between the small hole and the nozzle was sealed.
- a plurality of water absorption holes for absorbing water were provided on the side surface of the nozzle.
- a suction pump (PT09A-12-03) manufactured by CI Kasei Co., Ltd. was connected to the end of the nozzle led out of the casing.
- a fuel pump (personal pump NP-KX-100) manufactured by Nippon Seimitsu Kagaku Co., Ltd. was connected as a fuel supply unit to the fuel inlet of each cell arranged on the end face of the cell stack. Specifically, a silicon tube was inserted into the fuel inlet of each cell, and the silicon tube was joined by a branch pipe to form one flow path, and this flow path was connected to a fuel pump.
- a silicon tube was inserted into the oxidant inlet of each cell, and the silicon tube was joined by a branch pipe to form one flow path, and this flow path was connected to the mass flow controller.
- a rectangular parallelepiped polypropylene container having a bottom surface of 15 ⁇ 1 cm and a height of 3.5 cm was used as the drainage tank.
- a porous membrane Temisch manufactured by Nitto Denko Corporation was joined to the upper surface of the drainage tank by heat welding as a gas-liquid separation membrane.
- a polypropylene mixing tank with a capacity of 300 cm 3 was provided upstream of the fuel pump, and a cartridge-like fuel tank containing methanol as supplementary fuel was connected further upstream.
- the drainage tank and the mixing tank were connected by piping, and a pump manufactured by Nippon Seimitsu Kagaku Co., Ltd. was connected as a circulation pump in the middle of the piping.
- a silicon tube is inserted into the fuel outlet of each cell arranged on the other end face of the cell stack, and the silicon tube is joined by a branch pipe to form a single flow path. Connected to drain tank.
- the first opening of the casing of the gas-liquid separation mechanism produced above was directly connected to the oxidant outlets of the cells arranged on the same end face so as to block all the oxidant outlets.
- the suction pump outlet side connected to the nozzle inserted into the sponge in the gas-liquid separation mechanism was connected to the drainage tank via a pipe. In this way, a generated water discharge path including a nozzle, a suction pump, and piping was formed.
- the outputs of the fuel pump, circulation pump and suction pump were controlled by a microcomputer. Specifically, the output parameters of the fuel pump and the like were determined and controlled so that the fuel concentration in the mixing tank, which is the junction, was constant. Under the above control, a 4 mol / L aqueous methanol solution was supplied to the anode at a flow rate of 10 cm 3 / min. Non-humidified air was supplied to the cathode at a flow rate of 15000 cm 3 / min.
- the output terminal of the fuel cell was connected to an electronic load device (PLZ164WA) manufactured by Kikusui Electronics Corporation through a DC / DC converter.
- Example 1 A gas-liquid separation mechanism similar to that in Example 1 was prepared except that the entire surface of the porous filter (carbon sheet having a thickness of 4 mm) was coated with a water-absorbing material (natural sponge sheet having a thickness of 4 mm). A similar fuel cell system of Example 1 was produced and evaluated in the same manner. As a result, from the middle of continuous power generation, the entire surface of the porous filter was covered with a water-absorbing material retaining moisture, making it difficult to circulate air and increasing the pressure loss of the cathode. However, the degree of condensation was not generated on the porous filter.
- Example 2 A gas-liquid separation mechanism similar to that in Example 1 was prepared except that only a porous filter was used and no water-absorbing material was used. Using this, a fuel cell system similar to that in Example 1 was manufactured. Evaluated. In this comparative example, since the flexibility of the carbon sheet was insufficient, it was difficult to make the porous filter adhere to the exhaust port of the housing. As a result, although the cathode pressure loss was reduced, cathode generated water discharged from the oxidant outlet could not be efficiently recovered by the gas-liquid separation mechanism, resulting in dew condensation and a cell voltage drop.
- the fuel cell system of the present invention is useful as a power source in portable small electronic devices such as notebook personal computers, mobile phones, and personal digital assistants (PDAs). Further, the fuel cell system of the present invention can be applied to uses such as a power source for electric scooters. While this invention has been described in terms of the presently preferred embodiments, such disclosure should not be construed as limiting. Various changes and modifications will no doubt become apparent to those skilled in the art to which the present invention pertains after reading the above disclosure. Accordingly, the appended claims should be construed to include all variations and modifications without departing from the true spirit and scope of this invention.
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Abstract
Description
アノード: CH3OH+H2O→CO2+6H++6e-
カソード: (3/2)O2+6H++6e-→3H2O
ここで、気液分離機構は、酸化剤出口と外部とを連通する排気口と、排気口を塞ぐ多孔質フィルタと、多孔質フィルタの酸化剤出口側の表面を部分的に被覆する吸水性材料と、を有する。
本発明の新規な特徴を添付の請求の範囲に記述するが、本発明は、構成および内容の両方に関し、本発明の他の目的および特徴と併せ、図面を照合した以下の詳細な説明によりさらによく理解されるであろう。
燃料電池システム1が具備する燃料電池2は、本体2aと、液状燃料を導入する燃料入口2bと、燃料排液を放出する燃料出口2cと、酸化剤を導入する酸化剤入口2dと、未消費酸化剤および生成水を含む流体を放出する酸化剤出口2eとを有する。本体2aは、一般に、2以上のセルを電気的に直列に接続するように積層したスタックを含んでいる。
セル10は、直接メタノール型燃料電池のセルであり、高分子電解質膜12と、高分子電解質膜12を間に挟むように配置されたアノード14及びカソード16を含んでいる。高分子電解質膜12は、水素イオン伝導性を有している。アノード14には、燃料であるメタノールが供給される。カソード16には、酸化剤である空気が供給される。
気液分離機構100は、酸化剤出口2eと外部とを連通する排気口104と、排気口104を塞ぐ多孔質フィルタ105と、多孔質フィルタ105の酸化剤出口側の表面を部分的に被覆する吸水性材料106とを具備する。
例えばカーボン多孔体は、カーボン粉末とバインダとの混合物をシート状に成形することにより得られる。バインダの量は、成形されるシートが適度な細孔容積を有するように適宜調整される。カーボン粉末の粒度分布などの粉体物性についても、所望の平均細孔径や細孔容積に応じて適宜選択される。カーボンペーパ、カーボン不織布などは市販のものを使用できる。
排液タンク7は、例えば、上部に窓部113aを有する容器113を含み、その窓部113aを、二酸化炭素を通過させる気液分離膜114で塞ぐようにして構成される。気液分離膜114には、撥水性材料が好ましく用いられる。例えば、ポリテトラフルオロエチレンの粒子を溶着によりシート状に形成した材料などが用いられる。このような材料は、水蒸気を通過させるため、排液タンク7内の液量が過剰に多くなった場合には、排液タンク107を加熱などすると、気液分離膜を介して水分を水蒸気として外部に放出することができる。一方、排液タンク内の液量が過剰に少なくなると、補充燃料を希釈することが困難になるため、排液タンク107を冷却したり、気液分離機構100の吸引ポンプ111の出力を向上させたりして、液量を調整することが好ましい。排液タンク7には、液量センサとして一対の電極7aや、温度センサ115を設けることが好ましい。
(実施例1)
アノード触媒粒子と、それを担持する導電性の担体とを含むアノード触媒担持体を調製した。アノード触媒粒子としては、白金-ルテニウム合金(原子比1:1)(平均粒径:5nm)を用いた。担体としては、平均一次粒子径が30nmのカーボン粒子を用いた。白金-ルテニウム合金とカーボン粒子との合計重量に占める白金-ルテニウム合金の重量は、80重量%とした。
(アノードの形成)
アノード触媒担持体の10gと、パーフルオロカーボンスルホン酸/テトラフルオロエチレン共重合体(H+型)を含有する分散液(ナフィオン分散液、「Nafion(登録商標)5重量%溶液」、デュポン社製)の70gとを、適量の水とともに攪拌機により攪拌して混合した。この後、得られた混合物を脱泡して、アノード触媒層形成用インクを得た。
カソード触媒担持体の10gと、パーフルオロカーボンスルホン酸/テトラフルオロエチレン共重合体(H+型)を含有する分散液(前出の商品名「Nafion(登録商標)5重量%溶液」)の100gとを、適量の水とともに攪拌機により攪拌して混合した。この後、得られた混合物を脱泡して、カソード触媒層形成用インクを得た。
なお、アノード触媒層と、カソード触媒層とは、それぞれの中心(長方形の対角線の交点)が高分子電解質膜の厚さ方向に平行な1つの直線上に位置するように配置した。
以上のようにして、CCMを作製した。
(アノード多孔質基材の作製)
撥水処理が施されたカーボンペーパ(商品名「TGP-H-090」、厚さ約300μm、東レ(株)製)を、希釈されたポリテトラフルオロエチレン(PTFE)のディスパージョン(商品名「D-1」、ダイキン工業(株)製)に1分間浸漬した。次いで、そのカーボンペーパを、100℃に温度設定された熱風乾燥機中で乾燥させた。次いで、乾燥後のカーボンペーパを、電気炉中において、270℃で2時間焼成した。そのようにして、PTFEの含有量が10重量%であるアノード多孔質基材を得た。
撥水処理が施されたカーボンペーパに代えて、カーボンクロス(商品名「AvCarb(商標)1071HCB」、バラードマテリアルプロダクツ社製)を使用したこと以外は、アノード多孔質基材と同様にして、PTFEの含有量が10重量%であるカソード多孔質基材を作成した。
アセチレンブラックの粉末と、PTFEのディスパージョン(商品名「D-1」、ダイキン工業(株)製)とを攪拌機により攪拌して混合することにより、全固形分に占めるPTFEの含有量が10重量%であり、全固形分に占めるアセチレンブラックの含有量が90重量%である撥水層形成用インクを得た。得られた撥水層形成用インクを、エアーブラシを使用したスプレー法により、アノード多孔質基材の一方側の表面に吹き付けるようにして塗布した。その後、塗布されたインクを、100℃に温度設定された恒温槽内で乾燥させた。次いで、撥水層形成用インクを塗布したアノード多孔質基材を、電気炉により、270℃で2時間焼成して、界面活性剤を除去した。こうして、アノード多孔質基材上にアノード撥水層を形成し、アノード拡散層を得た。
カソード多孔質基材の一方の表面に、アノード撥水層と同様にして、カソード撥水層を形成し、カソード拡散層を得た。
得られた積層体を、温度を125℃に設定した熱プレス装置により、5MPaの圧力で1分間加圧した。これにより、アノード触媒層とアノード拡散層とを接合するとともに、カソード触媒層とカソード拡散層とを接合した。
以上のようにして、アノードと、高分子電解質膜と、カソードとからなる膜-電極接合体(MEA)を得た。
厚み0.25mmのエチレンプロピレンジエンゴム(EPDM)のシートを、50×120mmの長方形に裁断した。さらに、その中央部分を、シートに42×92mmの長方形の開口が形成されるようにくり抜いた。このようにして、2枚のガスケットを得た。
一方のガスケットの中央の開口部に、アノードを嵌め込むように配置し、他方のガスケットの中央の開口部に、カソードを嵌め込むように配置した。
アノード側セパレータの素材として、厚み1.5mm、サイズ50×120mmの長方形の樹脂含浸黒鉛板を準備した。その黒鉛板の表面を切削して、メタノール水溶液をアノードに供給する燃料流路を形成した。セパレータの短辺側端部の一方には、燃料流路の入口部(燃料入口)を配置した。セパレータの短辺側端部の他方には、燃料流路の出口部(燃料出口)を配置した。このようにして、アノード側セパレータを作製した。
以上のようにして、サイズが50×120mmであるDMFCのセルスタックを得た。
厚さ4mm、平均細孔径0.6mmの親水処理を施したカーボンシートを10mm×35mmの形状に切り抜き、多孔質フィルタを得た。多孔質フィルタと水との接触角は10°であった。
セルスタックの端面に配置された各セルの燃料入口に、燃料供給部として、日本精密科学(株)製の燃料ポンプ(パーソナルポンプNP-KX-100)を接続した。具体的には、各セルの燃料入口にそれぞれシリコンチューブを差し込み、分岐管によりシリコンチューブを合流させて一本の流路を形成し、この流路を燃料ポンプと接続した。
一方、同じ端面に配置された各セルの酸化剤出口には、総ての酸化剤出口を塞ぐように上記で作製した気液分離機構の筐体の第1開口を直接接続した。
燃料ポンプ、循環ポンプおよび吸引ポンプの出力は、マイクロコンピュータにより制御した。具体的には、合流部である混合タンク内の燃料濃度が一定になるように、燃料ポンプ等の出力パラメータを決定して制御した。
上記制御により、アノードには、4mol/Lのメタノール水溶液を、10cm3/minの流量で供給した。カソードには、無加湿の空気を、15000cm3/minの流量で供給した。燃料電池の出力端子は、DC/DCコンバータを介して、菊水電子工業(株)製の電子負荷装置(PLZ164WA)に接続した。200mA/cm2の一定の電流密度となるように調節して連続発電を行ったところ、気液分離機構の多孔質フィルタに結露は発生せず、良好な運転状態を維持できた。
以上のように、本発明によれば、カソードに酸化剤を送り込む際の圧力損失の増大が抑制される。
多孔質フィルタ(厚さ4mmのカーボンシート)の全面を吸水性材料(厚さ4mmの天然スポンジシート)で被覆したこと以外、実施例1と同様の気液分離機構を作製し、これを用いて、実施例1の同様の燃料電池システムを作製し、同様に評価した。その結果、連続発電の途中からは、多孔質フィルタの全面が、水分を保持した吸水性材料で被覆された状態となり、空気を流通させることが困難となり、カソードの圧力損失が増大した。ただし、多孔質フィルタに結露が発生するほどではなかった。
多孔質フィルタのみを用い、吸水性材料を用いなかったこと以外、実施例1と同様の気液分離機構を作製し、これを用いて、実施例1の同様の燃料電池システムを作製し、同様に評価した。本比較例においては、カーボンシートの柔軟性が不十分であったため、筐体の排気口に多孔質フィルタを密着させることが困難であった。その結果、カソードの圧力損失は低下したが、酸化剤出口から放出されるカソード生成水を気液分離機構で効率良く回収することができず、結露が発生し、セルの電圧低下を招いた。
本発明を現時点での好ましい実施態様に関して説明したが、そのような開示を限定的に解釈してはならない。種々の変形および改変は、上記開示を読むことによって本発明に属する技術分野における当業者には間違いなく明らかになるであろう。したがって、添付の請求の範囲は、本発明の真の精神および範囲から逸脱することなく、すべての変形および改変を包含する、と解釈されるべきものである。
2 燃料電池
2b 燃料入口
2c 燃料出口
2d 酸化剤入口
2e 酸化剤出口
3 燃料ポンプ
4 空気ポンプ
5 制御装置
6 燃料タンク
7 排液タンク
8 合流部
100 気液分離機構
101 生成水排水路
102 DC/DCコンバータ
103 蓄電池
104 排気口
105 多孔質フィルタ
106 吸水性材料
107 筐体
107a 第1開口
111 吸引ポンプ
112 ノズル
Claims (7)
- 少なくとも1つのセルと、液状燃料を導入する燃料入口と、燃料排液を放出する燃料出口と、酸化剤を導入する酸化剤入口と、未消費酸化剤および生成水を含む流体を放出する酸化剤出口と、を有する燃料電池と、
前記燃料入口に前記液状燃料を供給する燃料供給部と、
前記酸化剤入口に前記酸化剤を供給する酸化剤供給部と、
前記燃料排液と、前記生成水の一部と、を収容する排液タンクと、
前記燃料排液を前記排液タンクに導く燃料排出路と、
前記流体から前記生成水の一部を分離するとともに残部を外部に放出する気液分離機構と、
前記分離された生成水を前記排液タンクに導く生成水排出路と、を具備し、
前記気液分離機構は、
前記酸化剤出口と外部とを連通する排気口と、
前記排気口を塞ぐ多孔質フィルタと、
前記多孔質フィルタの前記酸化剤出口側の表面を部分的に被覆する吸水性材料と、を有する、直接酸化型燃料電池システム。 - 前記多孔質フィルタが、平均細孔径0.4~1.2mmの細孔を有する、請求項1記載の直接酸化型燃料電池システム。
- 前記多孔質フィルタが、カーボンシートからなる、請求項1または2記載の直接酸化型燃料電池システム。
- 前記カーボンシートには親水性が付与されている、請求項3記載の直接酸化型燃料電池システム。
- 前記多孔質フィルタの前記酸化剤出口側の表面の60~90%が、前記吸水性材料で被覆されている、請求項1~4のいずれかに記載の直接酸化型燃料電池システム。
- 前記生成水排出路が、前記吸水性材料に保持された前記生成水を吸引する吸引ポンプを具備する、請求項1~5のいずれかに記載の直接酸化型燃料電池システム。
- 前記燃料供給部は、
前記排液タンクから、前記燃料入口に、前記生成水で希釈された前記燃料排液を循環させる循環ポンプと、
補充燃料を含む燃料タンクと、
前記燃料タンクから供給される前記補充燃料を前記希釈された燃料排液と合流させる合流部と、を具備する、請求項1~6のいずれかに記載の直接酸化型燃料電池システム。
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DE112011100391T DE112011100391T5 (de) | 2010-06-29 | 2011-02-25 | Direktoxidationsbrennstoffzellensystem |
US13/390,042 US20120148928A1 (en) | 2010-06-29 | 2011-02-25 | Direct oxidation fuel cell system |
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JP2005238217A (ja) * | 2003-07-22 | 2005-09-08 | Matsushita Electric Ind Co Ltd | 気液分離器および燃料電池 |
JP2008311166A (ja) * | 2007-06-18 | 2008-12-25 | Panasonic Corp | 燃料電池システム |
JP2007311363A (ja) * | 2007-07-30 | 2007-11-29 | Sanyo Electric Co Ltd | 燃料電池システム |
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DE112011100391T5 (de) | 2012-12-06 |
JPWO2012001839A1 (ja) | 2013-08-22 |
US20120148928A1 (en) | 2012-06-14 |
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