JP4760469B2 - Humidifier and fuel cell system - Google Patents

Description

  The present invention relates to a humidifier provided with a water permeable membrane, and a fuel cell system provided with the humidifier.

  As a kind of humidifier for humidifying gas, conventionally, a humidifier provided with a water vapor permeable membrane that allows water vapor to permeate from a high water vapor partial pressure side to a low side has been used. As an example of a system using such a humidifier, in a fuel cell system, a high-humidity gas discharged from the fuel cell and a low-humidity gas to be supplied to the fuel cell are placed on each surface of the water vapor permeable membrane. On the other hand, a configuration is known in which a gas to be supplied to the fuel cell is humidified using a gas with high humidity (see, for example, cited document 1).

JP 2001-351660 A Japanese Patent Laid-Open No. 5-3918

  The efficiency of humidification using such a water vapor permeable membrane depends on the water vapor partial pressure difference between the high humidity gas which is the side that provides water vapor and the low humidity gas that is the side that receives the water vapor. When high humidity gas is supplied to one surface of the water vapor permeable membrane and low humidity gas is supplied to the other surface, the water vapor partial pressure of the high humidity gas gradually decreases on the water vapor permeable membrane, and the water vapor of the low humidity gas The partial pressure gradually increases. Therefore, in the water vapor permeable membrane, the water vapor partial pressure difference between the two surfaces differs depending on the location, and the water vapor transmission efficiency (water vapor transmission amount per unit area) becomes non-uniform in the surface. That is, in a place where the water vapor partial pressure difference between both surfaces of the water vapor permeable membrane is relatively small, the water vapor transmission efficiency is lowered, which is a factor that hinders the improvement of the humidifying efficiency in the entire water vapor permeable membrane.

  A similar problem can occur when liquid water and gas are brought into contact with each other through a water vapor permeable membrane to humidify the gas. As the gas partial pressure of the gas increases on the downstream side of the gas flow, the same problem occurs. Since it is difficult for water vapor to permeate, improvement in humidification efficiency has been desired.

  The present invention has been made in order to solve the above-described conventional problems, and an object of the present invention is to suppress a partial decrease in water vapor transmission efficiency in the water vapor permeable membrane and improve the humidification efficiency of the entire humidifier. .

In order to achieve the above object, a first gas humidifier of the present invention comprises:
An outer shell container that forms a space inside;
A membrane disposed in the outer shell container, wherein a space in the outer shell container is formed on one surface side and a first space in which a low-humidity humidified gas flows and on the other surface side. And a second space through which a high-humidity gas having a higher humidity than the humidified gas flows, and an amount of water vapor corresponding to a difference in water vapor partial pressure between both surfaces of the film is high. and a water vapor permeable membrane that to lower the humidified gas side of the water vapor partial pressure permeability umbrella from the humidity gas side,
The gist of the water vapor permeable membrane is that the region where the water vapor partial pressure difference between the first space and the second space is smaller is formed thinner.

  According to the first gas humidifier of the present invention configured as described above, the thickness of the water vapor permeable membrane is smaller in the region where the water vapor partial pressure difference between the first space and the second space is smaller. Since it is formed, the water vapor transmission amount can be increased even in the region where the water vapor partial pressure difference is small, and the humidification efficiency of the entire humidifier can be improved. At this time, the thickness of the water vapor permeable membrane is relatively thin in the region where the water vapor partial pressure difference is small, but the film thickness is relatively thick in the region where the water vapor partial pressure difference is large. It becomes possible to secure.

In the first gas humidifier of the present invention,
The water vapor permeable membrane has a thinner thickness in a region corresponding to a downstream side of the flow of the high-humidity gas in a region where the predetermined amount of the high-humidity gas supplied to the second space flows. It's also good.

  When a certain amount of high-humidity gas flows through the second space, the partial pressure of water vapor in the high-humidity gas decreases toward the downstream side, making it difficult to ensure a difference in partial pressure of water vapor between both surfaces of the water-vapor permeable membrane. However, even in such a case, it is possible to improve the water vapor transmission efficiency in such a region by reducing the thickness of the water vapor permeable membrane in a region where it is difficult to ensure the water vapor partial pressure difference.

The second gas humidifier of the present invention is
An outer shell container that forms a space inside;
A membrane disposed in the outer shell container, wherein a space in the outer shell container is formed on one surface side and a first space in which a low-humidity humidified gas flows and on the other surface side. And a second space through which a high-humidity gas having a higher humidity than the humidified gas flows, and an amount of water vapor corresponding to a difference in water vapor partial pressure between both surfaces of the film is high. It was from the humidity gas side to the low water vapor partial pressure the humidified gas side magnetic bulk, and a vapor permeable membrane having a number of micropores,
The water vapor permeable membrane has at least either a higher pore ratio or a fine pore having a larger pore diameter in a region where the difference in water vapor partial pressure between the first space and the second space is smaller. It may be either.

  According to the second gas humidifier of the present invention configured as described above, the water vapor permeation having a larger number of micropores as the water vapor partial pressure difference between the first space and the second space becomes smaller. Since the membrane has at least one of a higher pore ratio and fine pores with a larger pore diameter, the moisture vapor permeation amount is increased even in the region where the water vapor partial pressure difference is small, and humidification is performed. The humidification efficiency of the entire apparatus can be improved. In addition, at this time, the region where the pore ratio in the water vapor permeable membrane is relatively high or the pore diameter of the fine pores of the water vapor permeable membrane is relatively large is limited to the region where the water vapor partial pressure difference is small. It is possible to ensure the strength of the water vapor permeable membrane as a whole.

In the second gas humidifier of the present invention,
Does the water vapor permeable membrane have a higher aperture ratio in a region corresponding to the downstream side of the flow of the high humidity gas in a region where the constant amount of the high humidity gas supplied to the second space flows? It may be at least one of fine pores having a larger pore diameter.

  When a certain amount of high-humidity gas flows through the second space, the partial pressure of water vapor in the high-humidity gas decreases toward the downstream side, making it difficult to ensure a difference in partial pressure of water vapor between both surfaces of the water-vapor permeable membrane. However, even in such a case, in the water vapor permeable membrane in a region where it is difficult to ensure a water vapor partial pressure difference, the water vapor permeable membrane has at least one of a higher pore ratio and a fine pore having a larger pore diameter. As a result, the water vapor transmission efficiency in such a region can be improved.

In the first or second gas humidifier of the present invention,
In the second space, the high humidity gas flows in a certain direction from a single gas supply port formed in the outer shell container to a single gas discharge port formed in the outer shell container. It is also good.

  In such a case, in the first gas humidifier of the present invention, the thickness of the water vapor permeable membrane may be reduced as it is closer to the gas outlet. Further, in the second gas humidifier of the present invention, at the vicinity of the gas discharge port, at least one of the pore ratio in the water vapor permeable membrane is increased and the pore diameter of the micropores in the water vapor permeable membrane is increased. Just do it.

In the first or second gas humidifier of the present invention,
The direction of the flow of the humidified gas in the first space and the direction of the flow of the high-humidity gas in the second space may be opposed to each other.

  With such a configuration, the water vapor partial pressure difference between the high-humidity gas side and the low-humidity gas side can be ensured in a wider range of the water-vapor permeable membrane, so that the humidification efficiency can be improved.

The third gas humidifier of the present invention is
An outer shell container that forms a space inside;
A first space which is disposed in the outer shell container, and the space in the outer shell container is formed on one surface side, and a humidified gas having a water vapor partial pressure lower than a saturated vapor pressure is introduced and flows through the first space; And a second space formed on the other surface side through which the humidifying liquid water flows , wherein gas is present on one surface with the film interposed therebetween, and on the other surface A water vapor permeable membrane that permeates more water vapor from the liquid water side to the gas side as the water vapor partial pressure on the one surface is lower when liquid water is present ,
Wherein the water vapor permeable membrane as the first space side regions water vapor partial pressure is not high, and is summarized in that the thickness is thinner.

  According to the third gas humidifier of the present invention configured as described above, the water vapor partial pressure in the first space is high, and the water vapor partial pressure difference between the first space and the second space is ensured. The more difficult the region, the thinner the water vapor permeable membrane. Therefore, even in the region where the water vapor partial pressure becomes high, the amount of water vapor permeated can be increased to improve the humidification efficiency of the entire humidifier. At this time, the thickness of the water vapor permeable membrane is relatively thin in the region where the water vapor partial pressure is high, but the film thickness is relatively thick in the region where the water vapor partial pressure is low. It becomes possible to secure.

  In the third gas humidifier of the present invention, the humidifying fluid may be liquid water. With such a configuration, the second space side is the same as the state in which the water vapor partial pressure is maintained at the saturated vapor pressure. Therefore, the water vapor partial pressure difference is higher in the region where the water vapor partial pressure in the first space is higher. Get smaller. Therefore, the humidification efficiency of the entire humidifier can be improved by reducing the thickness of the water vapor permeable membrane in such a region.

In the third gas humidifier of the present invention,
In the first space, the humidified gas flows in a certain direction from a gas supply port formed in the outer shell container to a gas discharge port formed in the outer shell container,
The water vapor permeable membrane may be formed so as to be thinner in a region closer to the gas discharge port.

  With such a configuration, in the first space, the water vapor partial pressure is higher in a region closer to the gas discharge port. Therefore, in the water vapor permeable membrane, the water vapor transmission efficiency in the region where the water vapor partial pressure in the first space is increased can be improved by reducing the thickness in the region closer to the gas discharge port.

The fourth gas humidifier of the present invention is
An outer shell container that forms a space inside;
A first space which is disposed in the outer shell container, and the space in the outer shell container is formed on one surface side, and a humidified gas having a water vapor partial pressure lower than a saturated vapor pressure is introduced and flows through the first space; And a second space formed on the other surface side through which the humidifying fluid flows , wherein gas is present on one surface and the liquid is formed on the other surface through the film. When water is present, the lower the water vapor partial pressure on the one surface is, the more water vapor is allowed to permeate from the liquid water side to the gas side, and a water vapor permeable membrane having a large number of micropores is provided.
Wherein the water vapor permeable membrane, and summarized in that the higher the first area the partial pressure of water vapor space side is not high, is whether the at least one having larger micropores of pore diameter or has a higher aperture ratio To do.

  According to the fourth gas humidifier of the present invention configured as described above, the water vapor partial pressure in the first space is high, and the water vapor partial pressure difference between the first space and the second space is ensured. In the water vapor permeable membrane having a large number of micropores, the region that becomes difficult is at least one of a higher pore ratio and a micropore having a larger pore diameter. Therefore, even in the region where the water vapor partial pressure becomes high, the amount of water vapor permeated can be increased to improve the humidification efficiency of the entire humidifier. Further, at this time, the partial pressure of water vapor in the first space is high in the region where the pore ratio in the water vapor permeable membrane is relatively high or the pore diameter of the micropores of the water vapor permeable membrane is relatively large. Since it is limited to the region, it is possible to ensure the strength of the entire water vapor permeable membrane.

  In the fourth gas humidifier of the present invention, the humidifying fluid may be liquid water. With such a configuration, the second space side is the same as the state in which the water vapor partial pressure is maintained at the saturated vapor pressure. Therefore, the water vapor partial pressure difference is higher in the region where the water vapor partial pressure in the first space is higher. Get smaller. Therefore, the humidification efficiency of the entire humidifier can be improved by increasing the aperture ratio of the water vapor permeable membrane or increasing the pore diameter in such a region.

In the fourth gas humidifier of the present invention,
In the first space, the humidified gas flows in a certain direction from a gas supply port formed in the outer shell container to a gas discharge port formed in the outer shell container,
The water vapor permeable membrane may have at least one of a higher opening ratio and a fine pore having a larger pore diameter in a region closer to the gas discharge port.

  With such a configuration, in the first space, the water vapor partial pressure is higher in a region closer to the gas discharge port. Therefore, in the water vapor permeable membrane, the region closer to the gas discharge port has at least one of a higher opening ratio and a fine pore having a larger pore diameter, so that the water vapor content in the first space is increased. It is possible to improve water vapor transmission efficiency in a region where the pressure becomes high.

The first fuel cell system of the present invention comprises:
A gas humidifier according to any one of claims 1 to 10 ,
A solid polymer electrolyte fuel cell,
The gist is to use, as the humidified gas, a reaction gas for use in an electrochemical reaction in the fuel cell.

  According to the first fuel cell system of the present invention configured as described above, the humidifier of the present invention is used to humidify the reaction gas for use in the electrochemical reaction. The durability of the humidifying device to be configured can be improved.

The second fuel cell system of the present invention comprises:
A gas humidifier according to any one of claims 1 to 6,
A solid polymer electrolyte fuel cell,
As the humidified gas, a reaction gas for use in an electrochemical reaction in the fuel cell is used,
The gist is that exhaust gas discharged after being subjected to an electrochemical reaction in the fuel cell is used as the high-humidity gas.

  According to the second fuel cell system of the present invention configured as described above, the humidifier of the present invention is used to humidify the reaction gas for use in the electrochemical reaction. The durability of the humidifying device to be configured can be improved. At this time, since the reaction gas is humidified using the exhaust gas containing the generated water generated by the electrochemical reaction, it is not necessary to separately prepare a fluid for humidification, and the apparatus configuration can be simplified.

  The present invention can be realized in various forms other than the above, and can be realized in the form of a gas humidification method, for example.

Next, embodiments of the present invention will be described in the following order based on examples.
A. Overall configuration of the apparatus of the first embodiment:
B. Humidifier configuration:
C. Second embodiment:
D. Variations of the first and second embodiments:
E. Third embodiment:
F. Variations:

A. Overall configuration of the apparatus of the first embodiment:
FIG. 1 is a block diagram showing a schematic configuration of a fuel cell system 10 according to a first embodiment of the present invention. The fuel cell system 10 includes a fuel cell 22 that is a main body of power generation, a hydrogen tank 23 that stores hydrogen to be supplied to the fuel cell 22, and an air compressor 24 for supplying compressed air to the fuel cell 22. Yes. Here, the hydrogen tank 23 is connected to the anode of the fuel cell 22 by the hydrogen supply path 60, and hydrogen stored in the hydrogen tank 23 is supplied to the anode of the fuel cell 22 as fuel gas. The air compressor 24 is connected to the cathode of the fuel cell 22 by an oxidizing gas supply path 67, and the air taken in by the air compressor 24 is supplied as an oxidizing gas to the cathode of the fuel cell 22. The fuel cell 22 is a solid polymer type fuel cell, and includes a solid polymer electrolyte membrane showing good proton conductivity in a wet state as an electrolyte layer. The fuel cell 22 has a stack structure in which a plurality of single cells are stacked. Below, the flow of the gas in each part which comprises the fuel cell system 10, and the fuel cell system 10 is further demonstrated.

  The hydrogen tank 23 is, for example, a hydrogen cylinder that stores high-pressure hydrogen. Or it is good also as a tank which stores hydrogen by providing a hydrogen storage alloy inside and making it store in a hydrogen storage alloy. The hydrogen gas stored in the hydrogen tank 23 is discharged to the hydrogen supply path 60 connected to the hydrogen tank 23, and then adjusted (depressurized) to a predetermined pressure by the pressure adjusting valve 62, so that the fuel cell 22 serves as a fuel gas. Is supplied to the anode of each single cell.

  The anode exhaust gas discharged from the anode of the fuel cell 22 is guided to the anode exhaust gas path 63 and flows into the hydrogen supply path 60 again. Thus, the remaining hydrogen in the anode exhaust gas circulates in a flow path (hereinafter referred to as a circulation flow path) composed of a part of the hydrogen supply path 60, the anode exhaust gas path 63, and the flow path in the fuel cell 22. Then, it is again subjected to an electrochemical reaction. The pressure in the circulation channel is adjusted by the pressure regulating valve 62 so that the electrochemical reaction according to the load request can proceed, and the hydrogen tank 23 is passed through the pressure regulating valve 62 as the electrochemical reaction proceeds. To the circulation channel. In order to circulate the anode exhaust gas in the circulation channel, a hydrogen pump 65 is provided in the anode exhaust gas channel 63.

  The anode exhaust gas path 63 is provided with a gas-liquid separator 27. As the electrochemical reaction proceeds, water is generated at the cathode, and the generated water is also introduced into the fuel gas supplied to the anode side through the electrolyte membrane of the fuel cell 22. Further, in the gas flowing on the anode side, impurities such as nitrogen are also introduced from the cathode side through the electrolyte membrane. In the gas-liquid separator 27, the water vapor contained in the anode exhaust gas is condensed, and the valve 27 a provided in the gas-liquid separator 27 is opened to thereby open the anode exhaust gas containing the condensed water and impurities. A part of it is discharged to the outside.

  The air compressor 24 supplies pressurized air as an oxidizing gas to the cathode of the fuel cell 22 via the oxidizing gas supply path 67. The cathode exhaust gas discharged from the cathode is guided to the cathode exhaust gas path 68 and discharged to the outside. Here, in this embodiment, the oxidizing gas supply path 67 and the cathode exhaust gas path 68 are routed through the humidifier 25. In the humidifier 25, the oxidizing gas supply path 67 and the cathode exhaust gas path 68 are separated from each other by a water vapor permeable film, and the pressurized air supplied to the cathode is humidified using the cathode exhaust gas containing water vapor. Yes. In this way, by humidifying the oxidizing gas prior to supply to the fuel cell 22, the fuel cell 22 of this embodiment ensures a wet state of the solid polymer electrolyte membrane that is the electrolyte layer. The configuration of the humidifier 25 will be described in detail later.

  Furthermore, the fuel cell system 10 includes a control unit (not shown) that controls the movement of each unit of the fuel cell system 10. The control unit is configured as a logic circuit centered on a microcomputer, and includes a CPU, a ROM, a RAM, an input / output port, and the like. Then, detection signals of various sensors provided in the fuel cell system 10 and information on load requirements for the fuel cell 22 are acquired, and a fuel cell such as the pressure regulating valve 62, the air compressor 24, the hydrogen pump 65, or the valve 27a. A drive signal is output to each part related to power generation 22.

B. Humidifier configuration:
FIG. 2 is an explanatory diagram illustrating a schematic configuration of the humidifying device 25. The humidifier 25 is disposed in the outer shell container 28 that forms a space therein, and in the outer shell container 28, and divides the space in the outer shell container 28 into two spaces, and the water vapor from one surface side to the other. And a water vapor permeable membrane 30 that is permeable to the surface side. Here, the space formed on one surface side of the water vapor permeable membrane 30 is a high humidity gas flow path 32 through which high humidity gas with higher humidity flows, and the space formed on the other surface side of the water vapor permeable membrane 30. Is a humidified gas flow path 34 through which a humidified gas to be humidified is a low-humidity gas having a lower humidity.

  A gas supply port 36 and a gas discharge port 37 are formed on the wall surface of the outer shell container forming the high-humidity gas flow path 32 on one surface side of the water vapor permeable membrane 30. When the gas is supplied from the gas supply port 36, the gas flows in the constant direction toward the gas discharge port 37 in the high humidity gas flow path 32. As described above, since the humidifier 25 is connected in the middle of the cathode exhaust gas path 68, the cathode exhaust gas discharged from the fuel cell 22 becomes a high humidity gas via the gas supply port 36 as a high humidity gas. It flows into the flow path 32. Then, the gas is discharged from the high humidity gas flow path 32 through the gas discharge port 37.

  Further, a gas supply port 39 and a gas discharge port 38 are formed on the wall surface of the outer shell container that forms the humidified gas channel 34 on the other surface side of the water vapor permeable membrane 30. When the gas is supplied from the gas supply port 39, the gas flows in the humidified gas flow path 34 toward the gas discharge port 38 in a certain direction. As described above, since the humidifier 25 is connected in the middle of the oxidizing gas supply path 67, the air taken in by the air compressor 24 is the humidified gas via the gas supply port 39 as the humidified gas. It flows into the flow path 34. Then, the gas is discharged from the humidified gas passage 34 via the gas discharge port 38 and supplied to the fuel cell 22.

  Here, in the humidifier 25 of the present embodiment, the gas supply port 39 on the humidified gas channel 34 side is provided in the vicinity of the gas outlet 37 on the high humidity gas channel 32 side, and the humidified gas flow The gas discharge port 38 on the side of the passage 34 is provided in the vicinity of the gas supply port 36 on the side of the high humidity gas flow channel 32. Therefore, in the high-humidity gas channel 32 and the humidified gas channel 34, the direction of the gas flow is a counter flow. Thus, by making the flow of the high humidity gas and the flow of the humidified gas counter flow, in the water vapor permeable membrane, a region in which the water vapor partial pressure difference between both surfaces of the membrane is ensured to be water vapor permeable, Can be wider.

  The water vapor permeable film 30 is a film having a property of allowing water vapor to permeate from the side having a high water vapor partial pressure to the side having a low water vapor partial pressure between both surfaces according to the water vapor partial pressure difference. The water vapor permeable membrane 30 of the present embodiment is configured by a homogeneous membrane having high hygroscopicity. This homogeneous film is a substantially dense film having no fine pores of 1 nm or more and can retain water molecules and allow water molecules to permeate, but other gases such as oxygen and nitrogen are substantially It has the property of not transmitting light. Specifically, the homogeneous membrane is, for example, a fluorine-based or hydrocarbon-based solid polymer electrolyte that absorbs water vapor and exhibits high proton conductivity in a wet state, polyethylene oxide having a hygroscopic property, polyvinyl alcohol, cellulose ether. And non-electrolytic polymers such as starch. Here, when a predetermined gas is passed through each of the high-humidity gas channel 32 and the humidified gas channel 34, the water-vapor permeable membrane 30 absorbs water vapor in the high-humidity gas and enters a moisture-absorbing state. A difference in water vapor partial pressure occurs between both surfaces of the water vapor 30, and water vapor permeates from the high-humidity gas channel side to the humidified gas channel side.

  In particular, the water vapor permeable membrane 30 provided in the humidifying device 25 of this embodiment is characterized in that its film thickness changes in the plane. Specifically, the water vapor permeable membrane 30 is formed so as to have a larger film thickness in a region corresponding to the upstream side of the gas flow in the high-humidity gas flow path 32, and the film thickness is increased toward a region corresponding to the downstream side of the gas flow. It is formed so as to become thinner gradually.

  As described above, the permeation of water vapor from the high-humidity gas channel 32 side to the humidified gas channel 34 side via the water vapor permeable membrane 30 is performed according to the partial pressure difference of the water vapor. When the cathode exhaust gas flows into the high-humidity gas flow path 32, the cathode exhaust gas has a very high humidity because it contains a large amount of water produced by the electrochemical reaction. It has become. Then, when the cathode exhaust gas comes into contact with air having lower humidity through the water vapor permeable membrane 30, a large water vapor partial pressure difference occurs between both surfaces of the water vapor permeable membrane 30, and water vapor is actively transmitted from the cathode exhaust gas to the air. To do. At this time, the cathode exhaust gas flows in the high-humidity gas flow channel 32 while supplying water vapor to the humidified gas flow channel 34, so that the water vapor content in the cathode exhaust gas decreases. Thereby, in the high-humidity gas channel 32, the water vapor partial pressure in the cathode exhaust gas becomes lower at the downstream side, and it becomes difficult to secure a sufficient water vapor partial pressure difference from the humidified gas channel 34 side.

  Here, the water vapor permeable membrane 30 has a property that the water vapor permeation amount increases as the water vapor partial pressure difference between the two surfaces serving as the driving force for water vapor permeation increases, and the water vapor permeation efficiency increases as the film thickness decreases. ing. Therefore, in the water vapor permeable membrane 30 of the present embodiment in which the film thickness is thinner in the region corresponding to the downstream side of the high-humidity gas flow path 32, even if the water vapor partial pressure difference becomes smaller in such a region, A decrease in the amount can be suppressed. In the water vapor permeable membrane 30 that is a homogeneous membrane, the following equation is established. Here, the water vapor permeation coefficient is a constant representing the ease of water vapor permeation through the membrane, and the diffusion coefficient representing the ease of water diffusion within the membrane and the ease of water dissolution within the membrane. Expressed as the product of the solubility coefficient expressed. This water vapor transmission coefficient is a value determined by the material constituting the water vapor permeable membrane.

  Water vapor transmission rate (permeation flux) = (water vapor transmission coefficient) × (water vapor partial pressure difference) / (film thickness)

  In FIG. 2, the distribution of the transmission efficiency over the entire surface when water vapor permeates through the water vapor permeable membrane 30 from the high-humidity gas flow channel 32 to the humidified gas flow channel 34 according to the size of the arrow. It is expressed conceptually. As shown in FIG. 2, in the humidifier 25 having the water vapor permeable membrane 30 whose film thickness is smaller in the high humidity gas downstream region, the water vapor transmission efficiency is maintained at a high level even in the high humidity gas downstream region where the water vapor partial pressure difference is small. Be drunk.

  On the other hand, in the humidifying device 125 including the water vapor permeable film 130 having a substantially uniform film thickness on the entire surface, the state of transmission efficiency distribution over the entire surface when water vapor permeates through the water vapor permeable film 130. Is conceptually represented in FIG. 3 in the same manner as FIG. In FIG. 3, the same reference numerals are given to portions common to the humidifying device 25 of FIG. 2, and detailed description is omitted. When the film thickness of the water vapor permeable membrane is substantially uniform over the entire surface, the water vapor transmission rate decreases in the high humidity gas downstream region where the water vapor partial pressure difference becomes smaller. Here, in the humidifying apparatus in which the high-humidity gas and the humidified gas are counterflowed, the high-humidity gas downstream region corresponds to the humidified gas upstream region. Since the humidified gas is humidified as it flows downstream, the water vapor partial pressure is lower toward the upstream side. Thus, the water vapor partial pressure of the humidified gas is lower. It can contribute to increase the water vapor partial pressure difference. However, in such a humidifier, the water vapor partial pressure in the high-humidity gas in the high-humidity gas downstream region is increased by the water vapor permeation actively progressing in the high-humidity gas upstream region into which the high-humidity gas having a high water vapor partial pressure flows. Will drop significantly. As a result, in the downstream area of the high-humidity gas, the water vapor partial pressure difference is smaller and the water vapor transmission rate is lowered, although the water vapor partial pressure of the humidified gas is relatively low.

  According to the humidifying device 25 of the present embodiment configured as described above, the higher the humidity gas downstream region where the water vapor partial pressure difference between the high humidity gas channel 32 side and the humidified gas channel 34 side becomes smaller, Since the film thickness of the water vapor permeable film 30 is thin, the water vapor transmission rate in the high humidity gas downstream region can be further increased, and the humidification efficiency of the humidifier 25 as a whole can be improved.

  At this time, although the thickness of the water vapor permeable film 30 is made thinner in the downstream area of the high humidity gas, the film thickness is made thicker in the upstream area of the high humidity gas. Can be suppressed. Here, it is conceivable to improve the humidification efficiency in the humidifier by reducing the film thickness of the entire water vapor permeable membrane. However, since high gas pressure is applied to both surfaces of the water vapor permeable membrane, If the thickness is small, it may be difficult to ensure the strength of the water vapor permeable membrane. On the other hand, in this embodiment, in the region where the water vapor transmission efficiency can be secured without reducing the film thickness, that is, in the high humidity gas upstream region where a large water vapor partial pressure difference occurs, the film is not particularly reduced in thickness. By ensuring the strength and reducing the film thickness only on the downstream side, it is possible to achieve both the maintenance of the strength of the water vapor permeable membrane and the improvement of the humidification efficiency as an apparatus.

  In the embodiment, a polymer homogeneous membrane is used as the water vapor permeable membrane 30, but a different configuration may be used. For example, the water vapor permeable membrane 30 is made of a porous membrane (for example, a polymer porous membrane or an inorganic porous membrane made of polyethylene or the like) having a micropore having a porosity of 5 to 90% and a pore diameter of 0.001 to 10 μm. May be configured. Alternatively, it is constituted by a membrane substrate made of the above porous membrane and a moisture absorbing layer made of the above-mentioned homogeneous membrane formed on the membrane substrate, and water vapor is unidirectionally passed from the moisture absorbing layer side to the membrane substrate side. The water vapor permeable membrane 30 may be constituted by a composite membrane that is permeated. Even when these membranes are used, since the water vapor transmission efficiency is affected by the film thickness as well as the water vapor partial pressure difference between both surfaces of the membrane, by forming the film thickness thinner in the downstream region of the high humidity gas flow path, The same effect as in the first embodiment can be obtained. When the composite membrane is used as the water vapor permeable membrane 30, at least one of the membrane base material made of a porous membrane and the moisture absorption layer made of a homogeneous membrane is provided in the high humidity gas downstream region. What is necessary is just to form a layer thickness thinner.

  Here, the film thickness of the water vapor permeable membrane and the degree of change in the film thickness depend on the type of film used, the partial pressure difference of the water vapor between the gas flowing through both flow paths through the water vapor permeable film, Depending on the state of change in pressure, etc., the strength required for the water vapor permeable membrane may be taken into consideration, so that the water vapor permeable membrane can be set appropriately so that sufficient water vapor transmission efficiency can be realized in a wider range. What is necessary is just to set the film thickness of a water vapor permeable film, for example in the range of 10-1000 micrometers so that it may become thin gradually from the high humidity gas upstream to the downstream.

  Moreover, it is good also as using the water vapor permeable film which made the film thickness thin in steps instead of using the water vapor permeable film which made the film thickness gradually (uniformly) thin. That is, a certain range in the high-humidity gas flow direction may be a uniform film thickness, and a water vapor permeable membrane that gradually decreases in thickness toward the downstream side of the high-humidity gas flow may be used. The same effect can be obtained if the water vapor permeable membrane has a thinner film thickness in the region downstream of the high humidity gas flow.

C. Second embodiment:
FIG. 4 is an explanatory diagram showing a schematic configuration of the humidifying device 225 of the second embodiment. For example, the humidifier 225 can be used in place of the humidifier 25 in the fuel cell system 10 similar to the first embodiment. In the following description, the same reference numerals are assigned to parts common to the first embodiment, and detailed description thereof is omitted.

  The humidifying device 225 of the second embodiment has the same configuration as the humidifying device 25 of the first embodiment, except that a water vapor permeable membrane 230 is provided instead of the water vapor permeable membrane 30. The water vapor permeable membrane 230 is a porous membrane made of a polymer material such as polyethylene or an inorganic material, for example. FIG. 5 is a plan view schematically showing the distribution of micropores formed in the water vapor permeable membrane 230. The water vapor permeable membrane 230 is formed such that the opening ratio (pore area / membrane area) is higher in the downstream region of the high-humidity gas flow. Note that, in the water vapor permeable membrane 230, the aperture ratio is increased by increasing the density of micropores (the number of micropores per unit area). The water vapor permeable membrane made of a porous film has a property that the water vapor transmission efficiency increases as the pore ratio increases. Therefore, in the water vapor permeable membrane 230, in the region where the pore ratio is increased, the water vapor transmission rate is increased. Is promoted.

  According to the humidifying device 225 of the second embodiment configured as described above, the opening ratio in the water vapor permeable membrane 230, which is a porous membrane, is increased in the downstream region of the high humidity gas where the water vapor partial pressure difference becomes smaller. Therefore, the water vapor transmission amount can be increased in a region where the water vapor transmission hardly progresses due to the small water vapor partial pressure difference. Therefore, the humidification efficiency in the entire humidifier 225 can be increased. In FIG. 4, the state of transmission efficiency distribution over the entire surface when water vapor passes from the high-humidity gas flow channel 32 to the humidified gas flow channel 34 through the water vapor permeable membrane 230, that is, the entire surface. The manner in which the water vapor transmission efficiency is made uniform is conceptually represented by the size of the arrows.

  At this time, although the opening ratio in the water vapor permeable membrane 230 is higher in the downstream area of the high humidity gas, the opening ratio is lower in the upstream area of the high humidity gas. A decrease in strength as a whole can be suppressed. Here, a measure to improve the humidification efficiency in the humidifier by increasing the aperture ratio of the entire water vapor permeable membrane is also conceivable, but since the high gas pressure is applied to both surfaces of the water vapor permeable membrane, the entire water vapor permeable membrane If the aperture ratio is increased, it may be difficult to ensure the strength of the water vapor permeable membrane. On the other hand, in the present embodiment, in particular, in the region where the water vapor transmission efficiency can be ensured without increasing the aperture ratio, that is, in the upstream region of the high humidity gas where a large water vapor partial pressure difference occurs, the aperture ratio should be particularly increased. By ensuring the film strength and increasing the aperture ratio only on the downstream side, it is possible to achieve both the maintenance of the strength of the water vapor permeable membrane and the improvement of the humidification efficiency as an apparatus.

  In the second embodiment, the aperture ratio in the water vapor permeable membrane 230 is changed in the plane, but the pore diameter of the micropores provided in the water vapor permeable membrane may be changed in the plane. FIG. 6 is a schematic view of the micropores formed in the water vapor permeable membrane 330, which is used in place of the water vapor permeable membrane 230 in a humidifier similar to the humidifier 225, and the pore diameter of the micropores is changed in the plane. FIG. As shown in FIG. 6, the water vapor permeable membrane 330 is formed such that the pore diameter of the fine pores is larger in the downstream area of the high humidity gas. In this manner, the water vapor transmission efficiency in the water vapor permeable membrane can be improved also by providing fine holes having a large pore diameter. Therefore, by increasing the pore diameter of the fine pores in the downstream region of the high-humidity gas, it is possible to increase the water vapor transmission amount in the region where the water vapor partial pressure difference is small, and improve the humidification efficiency in the humidifier. At this time, since the region where the pore diameter of the fine pores of the water vapor permeable membrane is relatively large is limited to the high humidity gas downstream region, it is possible to ensure the strength of the water vapor permeable membrane as a whole. .

  In the water vapor permeable membrane 330, the density of micropores is made substantially uniform throughout the membrane, and the pore diameter of the micropores is changed. Therefore, the aperture ratio is also increased in the high humidity gas downstream region. On the other hand, the pore diameter may be increased in the high-humidity gas downstream region while reducing the density of the fine pores toward the downstream region of the high-humidity gas so that the opening ratio is substantially uniform throughout the membrane. In the water vapor permeable membrane, the water vapor transmission efficiency can be improved by increasing the aperture ratio, increasing the pore diameter, or at least one of them. Thus, when changing the pore ratio or the pore diameter, for example, the pore ratio (porosity) is 5 to 90%, and the water vapor transmission efficiency is improved when the pore diameter is in the range of 0.001 to 10 μm. The distribution state of pores (opening ratio and distribution state of pore diameter) may be appropriately varied within the plane in consideration of the degree to which the film is formed, the strength of the film, or the degree to which water vapor selectively permeates through the membrane.

  The distribution state of the pores in the water vapor permeable membrane can be detected, for example, by observing the surface of the membrane with an electron microscope. Alternatively, the water vapor permeable membrane is divided into a plurality of regions where the water vapor partial pressure difference is different in the humidifier, and measurement is performed by the gas adsorption method or the mercury intrusion method. The pore distribution can be determined.

  In the second embodiment, a porous membrane is used as the water vapor permeable membrane. However, a composite membrane in which a homogeneous layer is formed on a membrane substrate made of a porous membrane may be used. Also in this case, in the membrane substrate constituting the composite membrane, the same effect can be obtained by increasing the aperture ratio or increasing the pore diameter in the higher humidity gas downstream region.

  Further, instead of using the water vapor permeable membrane in which the pore ratio and the pore diameter are gradually (uniformly) changed, a water vapor permeable membrane in which the pore ratio and the pore diameter are changed stepwise may be used. That is, in a certain range in the high-humidity gas flow direction, the opening ratio and the pore diameter are constant, and the opening ratio increases stepwise and / or the pore diameter toward the downstream side of the high-humidity gas flow. You may use the water-vapor-permeable film | membrane which becomes large. Even with such a configuration, the same effect as in the second embodiment can be obtained.

D. Variations of the first and second embodiments:
(D-1) Modification 1:
In the first and second embodiments, since the high humidity gas is supplied only from the gas supply port 36 to the high humidity gas flow path 32 of the humidifier, the downstream side closer to the gas discharge port 37 has a higher humidity. The water vapor concentration in the gas decreases. On the other hand, in the humidifier, it is also possible to provide a plurality of gas supply ports in the flow direction of the high humidity gas and additionally supply the high humidity gas in the middle of the gas flow of the high humidity gas. A humidifier 425 which is an example of such a humidifier is shown in FIG. This humidifier 425 can be used in place of the humidifier 25 in the fuel cell system 10 similar to that of the first embodiment, for example. In the following description, the same reference numerals are assigned to parts common to the first embodiment, and detailed description thereof is omitted.

  The outer shell container 28 of the humidifier 425 is provided with two gas supply ports 45 and 46 that open in the middle of the flow of the high-humidity gas in addition to the gas supply port 36 similar to the humidifier 25 of the first embodiment. ing. Here, a first branch path 40 branches off from the cathode exhaust gas path 68 connected to the gas supply port 36, and the first branch path 40 further branches into second branch paths 41 and 42. The second branch path 41 is connected to the gas supply port 45, and the second branch path 42 is connected to the gas supply port 46. Therefore, in the humidifier 425, a part of the cathode exhaust gas is supplied from the gas supply port 36 into the high humidity gas flow path 32, and the remaining cathode exhaust gas is supplied from the gas supply ports 45 and 46 to the high humidity gas flow path. 32 is supplied in the middle of the gas flow at 32. In such a humidifier 425, from the upstream gas supply port to the vicinity of the adjacent downstream gas supply port, as in the first and second embodiments, humidification is performed from the high humidity gas channel 32 side. As water vapor permeates to the gas flow path 34 side, the water vapor partial pressure difference between both surfaces of the water vapor permeable membrane 430 gradually decreases. However, by additionally supplying the cathode exhaust gas in the middle of the gas flow of the high-humidity gas, the partial pressure of water vapor in the high-humidity gas flow path increases in the vicinity of the additionally supplied gas supply port.

  FIG. 8 is a plan view schematically showing the state of micropores in the water vapor permeable membrane 430 made of a porous membrane used in the humidifying device 425. The water vapor permeable membrane 430 has an increased hole ratio as the density of micropores gradually increases toward the downstream side of the high-humidity gas, but again in the vicinity of the gas supply port in the middle of additional supply of the high-humidity gas, The aperture ratio is reduced. Thus, even in the case where the water vapor partial pressure difference is increased in the middle of the gas flow, in a region where the constant amount of high humidity gas supplied to the high humidity gas flow path 32 flows and the water vapor partial pressure difference gradually decreases, By gradually increasing the aperture ratio in the water vapor permeable membrane, it is possible to increase the amount of water vapor permeated in the region where the water vapor partial pressure difference is small, thereby improving the humidification efficiency of the entire humidifier. In FIG. 7, the permeation efficiency when water vapor permeates from the high-humidity gas channel 32 to the humidified gas channel 34 is conceptually represented by the size of the arrow for the entire water vapor permeable membrane surface. As shown in FIG. 7, in the humidifier 425 provided with the water vapor permeable membrane 430, the water vapor transmission efficiency can be obtained even in a region where a certain amount of gas flows between adjacent gas supply ports and the partial pressure difference of the water vapor gradually decreases. Is kept at a high level.

  In FIG. 8, in the water vapor permeable membrane 430, the region between the gas supply port 36 and the gas supply port 45, the region between the gas supply port 45 and the gas supply port 46, the gas supply port 46 and the gas. The region between the discharge port 37 and the discharge port 37 is shown as having fine holes formed in the same pattern, but may have a different configuration. The distribution state of the water vapor partial pressure difference between the both surfaces of the water vapor permeable membrane 430 varies depending on the split ratio of the cathode exhaust gas when the cathode exhaust gas is supplied from the gas supply ports 36, 45, 46. Further, the water vapor transmission efficiency (water vapor transmission amount) varies depending on the gas pressure and gas temperature on both surfaces of the water vapor permeable membrane 430 in addition to the water vapor partial pressure difference. Therefore, considering these factors as appropriate, it is sufficient to increase the water vapor transmission rate in the entire membrane by increasing the aperture ratio in a region that is strongly influenced by the factor that lowers the water vapor transmission efficiency.

(D-2) Modification 2:
In the humidifiers of the first and second embodiments described above, the high-humidity gas and the humidified gas flow in the flow path in a fixed direction, but may have different configurations. For example, the flow of the high-humidity gas or the humidified gas in the flow path may be reversed in the middle of the flow path so that the high-humidity gas or the humidified gas flows in a U shape. A humidifier 525 which is an example of such a humidifier is shown in FIG. This humidifier 525 can be used in place of the humidifier 25 in the fuel cell system 10 similar to that of the first embodiment, for example. In the following description, the same reference numerals are assigned to parts common to the first embodiment, and detailed description thereof is omitted.

  The humidifier 525 includes a water vapor permeable membrane 530 in the outer shell container 28, whereby the space in the outer shell container 28 is divided into a space that becomes a high-humidity gas flow path 532 and a space that becomes a humidified gas flow path 534. It is divided into and. Here, the wall surface of the outer shell container 28 is provided with a gas supply port 536 and a gas discharge port 537 at positions close to each other, and a gas supply port 539 and a gas discharge port 538 at positions close to each other. ing. Therefore, in the high-humidity gas channel 532 and the humidified gas channel 534, the supplied gas flows in a substantially U shape. In the humidifier 525, a gas supply port 536 into which high humidity gas flows in and a gas discharge port 538 through which humidified gas flows out are provided close to each other, and a gas discharge port 537 through which high humidity gas flows out and humidified. A gas discharge port 538 through which gas flows is provided in close proximity. Therefore, the flow of the high humidity gas in the high humidity gas flow path 32 and the flow of the humidified gas in the humidified gas flow path 34 are opposed to each other.

  FIG. 10 is a plan view schematically showing the state of pore distribution in the water vapor permeable membrane 530 made of a porous membrane provided in such a humidifying device 525. In FIG. 10, the direction of the flow of the high-humidity gas is represented by the direction of the arrow attached to the broken line. Similarly to the water vapor permeable membrane 230 of the second embodiment, the water vapor permeable membrane 530 has a larger opening ratio by increasing the density of the fine pores in the downstream region of the high humidity gas. Therefore, it is possible to increase the water vapor permeation amount in the downstream region of the high-humidity gas where the water vapor partial pressure difference is reduced, and to improve the humidification efficiency of the entire humidifier.

(D-3) Modification 3:
In the humidifier 525, the flow direction of the high-humidity gas or the humidified gas in the gas flow path is formed in a U shape by providing the gas supply port and the gas discharge port close to each other. In other words, there is a possibility that the water vapor partial pressure difference is not as small on the surface of the water vapor permeable membrane as in the downstream region of the high-humidity gas. That is, by providing the gas supply port and the gas discharge port close to each other, the gas discharged from the gas flow path is generated without flowing into the space forming the gas flow path. In the deep part of the gas flow path, there is a possibility that the water vapor partial pressure is lower than the downstream side of the high humidity gas flow. In this way, at the back of the gas flow path where the water vapor partial pressure is low, the water vapor transmission efficiency is lower than in the high humidity gas downstream region. In the humidifying device 525 of FIG. 9, a water vapor permeable membrane having a uniform aperture ratio and pore diameter is provided instead of the water vapor permeable membrane 530, and the high humidity gas and the coating are supplied to the humidifier at a predetermined gas flow rate. FIG. 11 schematically shows an example of the result of supplying a humidified gas and examining the amount of permeated water per unit area in the entire water vapor permeable membrane. In FIG. 11, the distribution state of the permeated water amount in the water vapor permeable membrane is represented by connecting the parts having the same permeated water amount per unit area with a line. FIG. 11 shows a state where the amount of permeated moisture is larger in the upstream side of the gas supply / discharge port and in the upstream region of the high humidity gas, and the amount of transmitted water is smaller in the downstream side of the gas supply / discharge port and in the downstream region of the high humidity gas. In addition, in FIG. 11, the distribution state of the high-humidity gas flow rate on the water vapor permeable membrane surface is conceptually represented by the thickness of a broken line with an arrow.

  When the distribution state of the permeated water amount in the water vapor permeable membrane is in the state shown in FIG. 11, the region where the permeated water amount per unit area is smaller is the region where the water vapor partial pressure difference is smaller. A water vapor permeable membrane having a higher aperture ratio in such a region may be used. An example of such a water vapor permeable membrane is shown in FIG. Thus, not only in the downstream area of the high-humidity gas but also by examining the distribution state of the actual permeated water amount and setting the distribution ratio of the aperture ratio in accordance with the actual gas flow state, for example. In addition, the effect of improving the water vapor transmission efficiency can be enhanced in the entire water vapor permeable membrane.

  In Modifications 1 to 3, the water vapor transmission efficiency in the region where the water vapor partial pressure difference is reduced is improved by the distribution of the aperture ratio in the water vapor permeable membrane, but a different configuration may be used. For example, as in the first embodiment, the thickness of the water vapor permeable film may be made thinner as the water vapor partial pressure difference becomes smaller. Alternatively, in the water vapor permeable membrane, in a region where the water vapor partial pressure difference is small, in addition to increasing the aperture ratio, or instead of increasing the aperture ratio, the pore diameter may be increased. good.

E. Third embodiment:
FIG. 13 is an explanatory diagram showing a schematic configuration of the humidifying device 725 of the third embodiment. The humidifier 725 is provided in place of the humidifier 25 in a fuel cell system similar to the fuel cell system 10 of the first embodiment. Since the humidifier 725 has a configuration similar to that of the humidifier 25, common portions are denoted by the same reference numerals, and detailed description thereof is omitted.

  The humidifier 725 includes an outer shell container 28 that forms a space therein, and a water vapor permeable membrane 730 that is disposed in the outer shell container 28 and divides the space in the outer shell container 28 into two spaces. . Here, the space formed on one surface side of the water vapor permeable membrane 730 becomes a humidified gas flow path 34 through which the humidified gas to be humidified, that is, the air serving as the oxidizing gas flows, and the other side of the water vapor permeable membrane 730 is provided. The space formed on the surface side is a humidified liquid water flow path 732 through which humidified liquid water for humidifying the humidified gas flows.

  A gas supply port 39 and a gas discharge port 38 are formed on the wall surface of the outer shell container that forms the humidified gas channel 34 on one surface side of the water vapor permeable membrane 730. In the humidifier 725, when air is supplied from the gas supply port 39, this air flows in the humidified gas flow path 34 toward the gas discharge port 38 in a certain direction. The air humidified via the humidified gas channel 34 is supplied to the fuel cell 22.

  In addition, a liquid water supply port 736 and a liquid water discharge port 737 are formed on the wall surface of the outer shell container forming the humidifying liquid water channel 732 on the other surface side of the water vapor permeable membrane 730. In the humidifier 725, when liquid water is supplied from the liquid water supply port 736, the liquid water flows in the humidifying liquid water channel 732 toward the liquid water discharge port 737 in a certain direction. The fuel cell system of this embodiment includes a liquid water tank (not shown) connected to the liquid water supply port 736 by a liquid water supply path 768. The liquid water that has reached the liquid water discharge port 737 is discharged to the outside via the liquid water discharge path 769 or is collected in the liquid water tank.

  Note that it is desirable to use pure water as the liquid water to be used because it is not necessary to consider other components that permeate the water vapor permeable membrane 730, and it is not necessary to consider the precipitation of some components from the liquid water. Further, in the humidifier 725 of FIG. 13, the liquid water flows in a direction facing the humidified gas, but may flow in the same direction. Further, as the humidifying liquid water, liquid water replenished from the outside to the liquid water tank may be used, or liquid water obtained by collecting moisture from the gas discharged from the fuel cell with a condenser is used. May be.

  The water vapor permeable membrane 730 provided in the humidifier 725 is the same as the water vapor permeable membrane 30 of the first embodiment, except that the film thickness gradually decreases from the humidified gas upstream side to the downstream side. . In the case of using liquid water instead of using a high-humidity gas having a higher water vapor partial pressure than the gas to be humidified for humidification, as in this example, the liquid water side always has a saturated vapor pressure. This can be considered to be the same state, and there is no need to consider a decrease in the water vapor partial pressure on the humidifying liquid water side. Therefore, when the state of the water vapor permeable membrane is uniform throughout the membrane, the water vapor transmission efficiency in the humidifier 725 decreases as the humidified gas downstream region flows through the humidified gas whose vapor partial pressure has increased due to humidification. Become. In the present embodiment, since the thickness of the water vapor permeable film 730 is made thinner in the humidified gas downstream region, the water vapor transmission is further promoted in the humidified gas downstream region.

  According to the humidifying device 725 of the third embodiment configured as described above, the water vapor transmission rate increases in the humidified gas downstream region in which the water vapor partial pressure of the humidified gas increases (that is, the water vapor partial pressure difference becomes small). Since the thickness of the film 730 is reduced, it is possible to increase the moisture permeation amount in the downstream region of the humidified gas and to increase the humidification efficiency of the entire humidifier.

  Here, the water vapor permeable membrane used in the humidifier 725 may be constituted by the porous membrane or the composite membrane described above, in addition to the homogeneous membrane similar to the first embodiment. In any case, the same effect of increasing the water vapor permeation amount in the region where the partial pressure of water vapor in the humidified gas is increased by reducing the thickness of the water vapor permeable membrane in the downstream region of the humidified gas. can get.

  Alternatively, in the humidifier 725, in place of the water vapor permeable membrane 730, as in the second embodiment, a porous membrane or a composite membrane in which at least one of the aperture ratio and the pore diameter is different in the plane is used. A water vapor permeable membrane may be used. In this case, in the humidified gas downstream region, that is, the region where the water vapor partial pressure in the humidified gas is high, at least one of a higher pore ratio and a fine pore having a larger pore diameter should be used. Thus, the same effect can be obtained.

  In the third embodiment, the flow path facing the humidified gas flow path 34 is a humidified liquid water flow path 732 through which liquid water flows. However, as in the first and second embodiments, high humidity gas flows. A high humidity gas flow path 32 may be used. Even in this case, by reducing the film thickness in the humidified gas downstream region, or in the water vapor permeable membrane, in the humidified gas downstream region, a finer pore having a higher aperture ratio or a larger pore diameter is formed. By having at least one of them, it becomes possible to increase the water vapor transmission amount of the entire apparatus. For example, if the film thickness on the humidified gas downstream region (high humidity gas upstream region) side is reduced, the amount of water vapor permeation increases further in the region where the partial pressure difference of the water vapor is high but the water vapor partial pressure difference is high. To do. At this time, if the amount of water vapor transmission increases in the upstream region of the high humidity gas, the partial pressure of water vapor of the high humidity gas further decreases in the downstream region of the high humidity gas and the difference in water vapor partial pressure becomes smaller. In the humidified gas upstream region), since the water vapor transmission amount is originally small, the influence of the water vapor transmission amount decrease is small, and the effect of increasing the water vapor transmission amount is obtained as a whole. Alternatively, even when the humidified gas downstream region (high-humidity gas upstream region) in the water vapor permeable membrane has at least one of a higher pore ratio or a fine pore with a larger pore diameter, It is the same. However, as in the first and second embodiments, the film thickness is made thinner in the high-humidity gas downstream region (humidified gas upstream region) or the humidified gas downstream region (high-humidity gas upstream region) in the water vapor permeable membrane. The effect of increasing the amount of water vapor permeation of the entire apparatus is usually obtained more and more by setting at least one of a higher pore ratio and / or a fine pore having a larger pore diameter. This is because the water vapor transmission amount in the region where the water vapor partial pressure difference is originally large and the water vapor transmission amount is large is ensured as it is, and the water vapor transmission amount in the region where the water vapor partial pressure difference is originally small and the water vapor transmission amount is small further increases. .

F. Variations:
The present invention is not limited to the above-described examples and embodiments, and can be implemented in various modes without departing from the gist thereof. For example, the following modifications are possible.

F1. Modification 1:
In the first to third embodiments, air is used as the humidified gas and the oxidizing gas for supplying the fuel cell is humidified. However, different configurations may be used. For example, a fuel gas to be supplied to the fuel cell may be used as a humidified gas, and the fuel gas may be humidified using anode exhaust gas or liquid water as a high humidity gas. Alternatively, in order to humidify the reaction gas to be supplied to the fuel cell, a steam-containing gas other than the exhaust gas corresponding to the reaction gas may be used as the high humidity gas. In addition to the fuel cell system, the humidifier of the present invention may be applied to humidify gases other than the reaction gas supplied to the fuel cell. The present invention can be applied to any humidifier that supplies steam from a high-humidity gas or liquid water to a humidified gas via a water vapor permeable membrane.

F2. Modification 2:
In the first to third embodiments, the water vapor permeable film is a film having a flat surface, but water vapor permeable films having different shapes may be used. For example, the water vapor permeable membrane may be formed in a pleated shape so as to ensure a wider surface area through which water vapor can permeate.

  Alternatively, a water vapor permeable membrane having a shape other than the sheet shape may be used. For example, a hollow fiber can be used as the water vapor permeable membrane. In this case, a bundle of hollow fibers is housed in a predetermined outer shell container that forms a space inside to constitute a humidifier, and a humidified gas is placed in either the inner space or the outer space of the hollow fiber. And a high humidity gas or a liquid for humidification may be flowed to the other side. At this time, the configuration of the present application can be realized by changing the film thickness, hole ratio, or pore diameter of the hollow fiber in accordance with the flow direction of the humidified gas or the like.

It is a block diagram showing the schematic structure of the fuel cell system of an Example. 3 is an explanatory diagram illustrating a schematic configuration of a humidifying device 25. FIG. It is explanatory drawing which represents notionally the mode of distribution of the water vapor transmission efficiency in the water vapor transmission film | membrane in which the film thickness was formed substantially uniformly on the whole surface. It is explanatory drawing showing schematic structure of the humidification apparatus 225 of 2nd Example. 4 is a plan view schematically showing the distribution of micropores formed in the water vapor permeable membrane 230. FIG. The top view which represents typically the mode of the micropore formed in the water vapor permeable film 330 which replaced with the water vapor permeable film 230 in the humidifier similar to the humidifier 225, and changed the pore diameter of the micropore in the surface. It is. It is explanatory drawing showing the schematic structure of the humidifier 425. FIG. 6 is a plan view schematically showing a state of fine holes in a water vapor permeable membrane 430. It is explanatory drawing showing the schematic structure of the humidifier 525. 4 is a plan view schematically showing the state of pore distribution in a water vapor permeable membrane 530. FIG. It is explanatory drawing showing an example of the result of having investigated the permeation | transmission water | moisture amount per unit area in the water vapor permeable membrane with a uniform pore ratio and pore diameter. 6 is a plan view schematically showing the state of pore distribution in a water vapor permeable membrane 630. FIG. It is explanatory drawing showing schematic structure of the humidification apparatus 725 of 3rd Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Fuel cell system 22 ... Fuel cell 23 ... Hydrogen tank 24 ... Air compressor 25, 125, 225, 425, 525, 725 ... Humidifier 27 ... Gas-liquid separator 27a ... Valve 28 ... Shell container 30, 130, 230 , 330, 430, 530, 630, 730 ... water vapor permeable membrane 32, 532 ... high humidity gas passage 34, 534 ... humidified gas passage 36, 39, 45, 46, 536, 539 ... gas supply port 37, 38 , 537, 538 ... gas discharge port 40 ... first branch passage 41, 42 ... second branch passage 45, 46 ... gas supply port 60 ... hydrogen supply passage 62 ... pressure regulating valve 63 ... anode exhaust gas passage 65 ... hydrogen pump 67 ... Oxidizing gas supply path 68 ... Cathode exhaust gas path 732 ... Humidification liquid water path 736 ... Liquid water supply port 737 ... Liquid water discharge port 768 ... Liquid water supply path 769 ... Liquid Discharge path

Claims (12)

A gas humidifier for humidifying gas,
An outer shell container that forms a space inside;
A membrane disposed in the outer shell container, wherein a space in the outer shell container is formed on one surface side and a first space in which a low-humidity humidified gas flows and on the other surface side. And a second space through which a high-humidity gas having a higher humidity than the humidified gas flows, and an amount of water vapor corresponding to a difference in water vapor partial pressure between both surfaces of the film is high. and a water vapor permeable membrane that to lower the humidified gas side of the water vapor partial pressure permeability umbrella from the humidity gas side,
The humidifying device is configured such that the water vapor permeable membrane is thinner in a region where a water vapor partial pressure difference between the first space and the second space becomes smaller. A gas humidifier according to claim 1,
The water vapor permeable membrane has a thinner thickness in a region corresponding to a downstream side of the flow of the high-humidity gas in a region where the predetermined amount of the high-humidity gas supplied to the second space flows. Humidifier. A gas humidifier for humidifying gas,
An outer shell container that forms a space inside;
A membrane disposed in the outer shell container, wherein a space in the outer shell container is formed on one surface side and a first space in which a low-humidity humidified gas flows and on the other surface side. And a second space through which a high-humidity gas having a higher humidity than the humidified gas flows, and an amount of water vapor corresponding to a difference in water vapor partial pressure between both surfaces of the film is high. It was from the humidity gas side to the low water vapor partial pressure the humidified gas side magnetic bulk, and a vapor permeable membrane having a number of micropores,
The water vapor permeable membrane has at least either a higher pore ratio or a fine pore having a larger pore diameter in a region where the difference in water vapor partial pressure between the first space and the second space is smaller. Is a humidifier. A gas humidifier according to claim 3,
Does the water vapor permeable membrane have a higher aperture ratio in a region corresponding to the downstream side of the flow of the high humidity gas in a region where the constant amount of the high humidity gas supplied to the second space flows? A humidifier that has at least one of fine pores having a larger pore diameter. A gas humidifier according to claim 2 or 4,
In the second space, the high-humidity gas flows in a certain direction from a single gas supply port formed in the outer shell container to a single gas discharge port formed in the outer shell container. apparatus. A gas humidifier according to any one of claims 1 to 5,
The humidifying device is a direction in which the direction of the flow of the humidified gas in the first space and the direction of the flow of the high-humidity gas in the second space are opposed to each other. A gas humidifier for humidifying gas,
An outer shell container that forms a space inside;
A first space which is disposed in the outer shell container, and the space in the outer shell container is formed on one surface side, and a humidified gas having a water vapor partial pressure lower than a saturated vapor pressure is introduced and flows through the first space; And a second space formed on the other surface side through which the humidifying liquid water flows , wherein gas is present on one surface with the film interposed therebetween, and on the other surface A water vapor permeable membrane that permeates more water vapor from the liquid water side to the gas side as the water vapor partial pressure on the one surface is lower when liquid water is present ,
Wherein the water vapor permeable membrane, the first as the water vapor partial pressure is not high region of space side, humidifier thickness is formed thinly. The gas humidifying device according to claim 7 Symbol mounting,
In the first space, the humidified gas flows in a certain direction from a gas supply port formed in the outer shell container to a gas discharge port formed in the outer shell container,
The moisture vapor permeable membrane is formed with a thinner thickness in a region closer to the gas discharge port. A gas humidifier for humidifying gas,
An outer shell container that forms a space inside;
A first space which is disposed in the outer shell container, and the space in the outer shell container is formed on one surface side, and a humidified gas having a water vapor partial pressure lower than a saturated vapor pressure is introduced and flows through the first space; And a second space formed on the other surface side through which the humidifying fluid flows , wherein gas is present on one surface and the liquid is formed on the other surface through the film. When water is present, the lower the water vapor partial pressure on the one surface is, the more water vapor is allowed to permeate from the liquid water side to the gas side, and a water vapor permeable membrane having a large number of micropores is provided.
Wherein the water vapor permeable membrane, the higher the first area the partial pressure of water vapor space side is not high, the humidifier is whether the at least one having larger micropores of pore diameter or has a higher aperture ratio. The gas humidifying device according to claim 9 Symbol mounting,
In the first space, the humidified gas flows in a certain direction from a gas supply port formed in the outer shell container to a gas discharge port formed in the outer shell container,
The humidifying apparatus, wherein the water vapor permeable membrane has at least one of a higher opening ratio and a fine pore having a larger pore diameter in a region closer to the gas discharge port. A fuel cell system,
A gas humidifier according to any one of claims 1 to 10 ,
A solid polymer electrolyte fuel cell,
A fuel cell system that uses a reaction gas for an electrochemical reaction in the fuel cell as the humidified gas. A fuel cell system,
A gas humidifier according to any one of claims 1 to 6,
A solid polymer electrolyte fuel cell,
As the humidified gas, a reaction gas for use in an electrochemical reaction in the fuel cell is used,
A fuel cell system that uses exhaust gas discharged after being subjected to an electrochemical reaction in the fuel cell as the high-humidity gas.

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