filling recycling device for fuel cell, fuel cell system and regenerator for filling recycling device

Filling recovery device for fuel cell, fuel cell system and regenerator for filling recovery device for fuel cell

Technical field

The present invention relates to a fuel cell filling and recovering device connected to a fuel cell system that directly supplies organic fuels such as methanol to an anode to generate electricity, a fuel cell system connected to the fuel cell filling and recovering device, and the fuel cell filling and recovering device The regenerative fuel cell is used to fill the regenerator with the regenerator.

Background technique

As the next generation of clean and efficient energy sources, fuel cell systems are eye-catching. Among them, a polymer electrolyte fuel cell (PEFC: Polymer Electrolyte Fuel Cell) in which an anode and a cathode are arranged with a polymer electrolyte sandwiched therebetween is attracting attention in applications such as power supplies for electric vehicles or distributed power supplies for households. In the solid polymer electrolyte fuel cell, a fuel cell that directly supplies organic fuels such as methanol or dimethyl ether to the anode to generate electricity, such as a direct methanol fuel cell (DMFC: Direct Methanol Fuel Cell), does not require the use of organic fuels such as methanol. A reformer that is reformed into a hydrogen-rich gas, so the structure becomes simple, and it is attracting attention in the use of portable instruments, and development is progressing.

The direct methanol fuel cell generates electricity according to the following reaction.

Anode: Cathode: From the above reaction, it can be seen that three times the amount of water consumed by the anode is generated in the cathode. Therefore, it is necessary to treat the water generated in the cathode.

However, this type of fuel cell has the following problems due to the need to treat the water generated in the cathode.

First, as the first problem, when water is discharged to the outside of the portable device, water or water vapor is released, so there is a problem that water droplets adhere to the portable device. In addition, when the fuel cell is in operation, for example, when the portable device is stored in a leather bag or a pocket, the leather bag or the pocket becomes wet.

In order to solve the first problem, a structure is proposed to provide an elastic membrane in the fuel tank, and store fuel on the side where the pressure of the elastic membrane acts. Through the consumption of fuel, the part of the fuel tank that becomes negatively pressured contains the generated water. Fuel cells (for example, JP 4-223058 A).

In addition, it has been proposed to form a bag-shaped separator in the fuel tank to house a fuel cell that produces water (for example, Japanese Patent Laid-Open No. 2003-92128).

However, in each of the above proposals, it is undeniable that the structure of the fuel cartridge has become complicated, and the manufacturing cost of the fuel cartridge has increased. In the above proposals, the recycling of fuel tanks is not considered. That is, in the proposal of Japanese Patent Laid-Open No. 4-223058, when the fuel container is replaced, the produced water and each fuel container are discarded. In Japanese Patent Laid-Open No. 2003-92128, a super absorbent material is used for the recovery of produced water. Its regeneration is difficult. Therefore, in these fuel containers, even if the produced water can be recovered, the fuel containers are discarded after use, and the cost during use increases.

In addition, in the direct methanol fuel cell, a method of supplying methanol, which is a fuel, has not been established. For example, in the method of installing a fuel container on a fuel cell and replacing the fuel container every time the fuel is consumed, the above-mentioned cost problem arises. Therefore, it is necessary for the user to supply methanol to the fuel container or fuel cell. However, it is well known that methanol is toxic. For example, when methanol is manually injected into a fuel container, it may leak, adhere to the user's skin, or inhale methanol vapor, which may cause adverse effects on the human body.

As a second problem, in order to perform continuous power generation, it is necessary to install auxiliary equipment for processing carbon dioxide and water generated in the cathode.

As such a conventional fuel cell system structure of the DMFC method, it is described in the specification of U.S. Patent No. 5,599,638 and the like. The fuel cell system uses a pump to supply methanol aqueous solution to the anode in order to stably supply methanol from a circulation container containing a methanol aqueous solution as a fuel to the anode, and recover the remaining methanol aqueous solution that is not consumed in the anode to the circulation container. , And then used as fuel for the fuel cycle.

The water generated by power generation on the anode side is recovered by the water recovery device and supplied to the circulation container containing the methanol aqueous solution.

However, in such a DMFC, as shown in the chemical formula, 1 mol of methanol and 1 mol of water in the methanol aqueous solution supplied to the anode side are consumed to generate electricity, and 3 mol of water is generated on the cathode side. Therefore, if all the generated water is recovered and supplied to the circulation container, the concentration of the methanol aqueous solution in the circulation container will be significantly reduced, and there will be a problem that the power generation time will be reduced or the power generation will be reduced.

Considering that only a part of the water generated on the cathode side is supplied to the circulation container, the method to prevent the concentration of the methanol aqueous solution from significantly decreasing, although such a method can be used as a fuel cell system for automobiles or large-scale equipment, there are It is necessary to drain other water that is not recovered in the circulation container. With this drain, the water adheres to the electronic devices or circuits built in the portable electronic device, or condensation may occur, and there is a fuel cell system that cannot be used as a portable electronic device. And the question of adoption.

In addition, fuel cell systems used in portable electronic devices must be miniaturized, and the amount of electricity generated is also small. In addition, self-consumption is used to drive auxiliary equipment such as pumps in the fuel cell system. Therefore, with limited electric energy, it is necessary for such auxiliary equipment to suppress power consumption as much as possible. For example, if the power generation output of the fuel cell system is 12W, it is desirable that the power consumption of the auxiliary machine be 2W or less.

However, in the above-mentioned conventional method, many auxiliary equipment such as a fuel supply device for supplying fuel (for example, a fuel supply pump) or a water recovery device for recovering water (for example, a water recovery pump) are required, and it is not only impossible to reduce the Self-consumption of electricity, and the system itself becomes complicated, there is a problem that it is difficult to miniaturize.

Therefore, the technical problem to be solved by the present invention is to realize the miniaturization and simplification of the auxiliary equipment structure such as the fuel supply system in a fuel cell that generates electricity while directly supplying liquid fuel such as methanol to the anode, and provides energy Regenerators for fuel cell refills, fuel cell systems, and regenerators for fuel cell refills used in portable electronic devices such as personal computers and mobile phones.

Summary of the invention

In order to achieve the above-mentioned object, the present invention is configured as follows.

According to a first aspect of the present invention, there is provided a filling recovery device for a fuel cell used in a fuel cell system provided with a fuel cell main body having an anode, a cathode, and an electrolyte membrane arranged between the anode and the cathode , Including: a container capable of forming a filling fuel storage space for accommodating the liquid fuel stock solution provided to the anode side, and the discharge recovery space for accommodating the discharge generated by the cathode;

The partition is configured to be movable along the axial direction inside the container, and divide the inside of the container into the filling fuel storage space and the discharge recovery space; they are respectively provided in the container and the discharge recovery space Communicating with the fuel cell main body for taking in the discharge inlet of the discharge containing water and air from the cathode side; communicating with the filling fuel storage space, and storing the liquid stored inside The fuel stock solution is supplied to the fuel supply port on the anode side of the fuel cell body; the pressure drop of the filling fuel storage space generates between the filling fuel storage space and the exhaust recovery space The pressure difference caused the partition to move, so that the filling fuel storage space is narrowed, and the liquid fuel material is fed from the filling fuel storage space through the fuel supply port, and taken from the exhaust The inlet recovers the exhaust generated on the side of the cathode to the exhaust recovery space.

According to the stated structure, a partition that can move axially is provided in the filling and recovery container to form a fuel storage space and an exhaust recovery space. The pressure difference between the fuel storage space and the exhaust recovery space is used to move the partition, and The fuel filling operation of the fuel container in the fuel cell system and the recovery operation of the effluent from the effluent container in the fuel cell system are performed in parallel in the same process. Therefore, the operation time of fuel filling and exhaust recovery is shortened, and rapid operation becomes possible.

According to a second embodiment of the present invention, there is provided a filling recovery device for a fuel cell, in a fuel cell system provided with a fuel cell main body having an anode, a cathode, and an electrolyte membrane arranged between the anode and the cathode The use includes: a container capable of forming a filling fuel storage space for accommodating the liquid fuel stock solution supplied to the anode side, and the discharge recovery space for accommodating the discharge generated by the cathode; arranging inside the container It is movable along the axial direction to divide the interior of the container into the filling fuel storage space and the effluent recovery space; the partitions are respectively provided in the container and communicate with the effluent recovery space, An effluent intake port for taking in effluent containing water and air from the cathode side of the fuel cell main body; supplying the water stored in the effluent recovery space to the fuel cell main body The water supply port on the anode side of the fuel cell; and the fuel supply port on the anode side of the fuel cell main body that communicates with the fuel storage space for filling and supplies the liquid fuel stock solution stored inside to the fuel supply port on the anode side of the fuel cell body,

Due to the exhaust that passes through the exhaust intake and is stored in the exhaust recovery space, the pressure in the exhaust recovery space becomes higher than the pressure in the filling fuel storage space, and the partition The plate moves to the side of the fuel storage space for filling and pressurizes the fuel storage space for filling, so that the liquid fuel stock solution can be discharged from the fuel supply port and the water can be discharged from the water supply port. .

According to the second aspect of the present invention, the fuel cell filling and recovering device has a fuel supply port to the fuel cell body, and the effluent recovery space and the filling fuel storage space are completely separated by the separator, so that the liquid fuel stock solution and the effluent are not mixed, Therefore, the concentration of the liquid fuel does not change. In addition, by using the exhaust stored in the exhaust recovery space, the separator is pressurized from the exhaust recovery space to the side of the fuel storage space for filling, and the pump for supplying fuel to the fuel cell body is not installed, which can stably The liquid fuel is supplied to the main body of the fuel cell.

The separator is pressurized by the discharge containing water and air from the cathode, and a separate pressurizing mechanism is not required in the fuel cell filling and recovering device, and the structure in the fuel cell filling and recovering device can be simplified. According to this, it is possible to prevent the internal structure of the fuel cell filling and recovering device from being complicated. In addition, the effluent is guided to the effluent recovery space at a time, and the amount of water consumed in the reaction of the anode is supplied from the effluent recovery space, so the fuel concentration on the anode side is not reduced, and excess water is not removed. Released to the outside, it can become a completely closed system.

In the filling recovery device for fuel cells, it is possible to install the separation of water and air from the exhaust in the exhaust recovery space, store the water in the exhaust recovery space, and discharge the air to the exhaust The gas-liquid separation mechanism discharged from the outside of the recovery space.

In addition, the gas-liquid separation mechanism may be provided with a pipe body communicating with the discharge inlet and arranged in the discharge recovery space, and the water recovered in the discharge recovery space may be used as a cooling medium, and the The water contained in the effluent is condensed into liquid water by a heat exchanger.

In addition, in the fuel cell filling and recovering device, a pressure adjusting mechanism that adjusts the pressure in the exhaust collecting space based on the exhaust from the fuel cell main body may be provided in the exhaust collecting space, and the pressure adjusting mechanism can be controlled by The pressure regulating valve and the like are arranged on the outer wall of the discharge recovery space.

In addition, as a third aspect of the present invention, there is provided the fuel cell filling and recovering device according to the above-mentioned embodiment 1 or 2, wherein the container is provided with a fuel replenishing device communicating with the filling fuel storage space. The fuel replenishment connector of the effluent recovery space, and the water recovery connector provided in communication with the effluent recovery space for recovering the effluent stored in the effluent recovery space; The regenerator for replenishing fuel in the storage space is connected to the water recovery connector and the fuel replenishing connector. By replenishing fuel to the fuel storage space for filling, the partition is moved in the direction of the exhaust recovery space to remove The effluent recovers the effluent in the space.

In addition, as a fourth aspect of the present invention, there is provided a fuel cell system including: the first aspect of the fuel cell reclaimer; an anode that oxidizes fuel, a cathode that reduces oxygen, and is arranged between the anode and the The electrolyte membrane between the cathodes and the fuel cell main body of the diffusion layer arranged on each surface of the electrolyte membrane; the liquid fuel stock solution contained in the filling fuel storage space is supplied to the anode, and the anode is connected The fuel supply port and the fuel supply pipe of the anode; the exhaust recovery pipe that can recover the exhaust from the cathode to the exhaust recovery space, and connects the cathode and the exhaust intake; A pressure difference generating mechanism that generates a pressure difference between the filling fuel storage space and the exhaust recovery space, thereby reducing the pressure of the filling fuel storage space.

As a fifth aspect of the present invention, a fuel cell system according to the fourth aspect includes an anode that oxidizes fuel, a cathode that reduces oxygen, an electrolyte membrane arranged between the anode and the cathode, and The main body of the fuel cell of the diffusion layer on each surface of the electrolyte membrane; the water contained in the exhaust can be supplied to the anode, and the water supply pipe connecting the water supply port and the anode; adjusting from the The first supply amount adjustment device that controls the amount of water delivered from the water supply port to make the fuel concentration supplied to the anode become a given value; the control device that controls the first supply amount adjustment device, according to the control device, uses the storage In the exhaust in the exhaust recovery space, the partition pressurizes the filling fuel storage space with a given pressure.

In each of the above-mentioned structures, various structures can be adopted for the pressure difference generating mechanism.

A sixth aspect of the present invention provides the fuel cell system according to the fourth or fifth aspect, wherein the pressure difference generating mechanism has an air pump that supplies air to the cathode;

The air pump supplies air to the cathode so that the exhaust generated in the cathode is recovered into the exhaust recovery space through the exhaust recovery pipe, and the exhaust recovery space is added Pressure, the separator is moved to the side of the filling fuel storage space, and the liquid fuel stock solution is supplied to the anode from the filling fuel storage space through the fuel supply pipe.

According to the above aspect, the air supply device is capable of moving the separator from the exhaust recovery space to the side of the filling fuel storage space, supplying the liquid fuel stock solution from the filling fuel storage space to the anode, and supplying air into the cathode. Air pump. That is, the air pump is an air supply pump that supplies air with such a pressure as the discharge pressure, and can simultaneously perform recovery of the discharge portion and replenishment of liquid fuel.

A seventh aspect of the present invention provides the fuel cell system according to the fifth aspect, further comprising: a second supply amount adjustment device that adjusts the amount of liquid fuel supplied to the fuel cell main body; and the control device controls the second supply amount An adjustment device that supplies the fuel consumed by power generation in the fuel cell main body from the fuel cell reclaimer to the anode side of the battery main body.

According to the above configuration, the second supply amount adjustment means controls to supply the consumed part of the fuel, so stable power generation can be performed.

An eighth aspect of the present invention provides the fuel cell system according to the fifth aspect, including: a position detection device that detects the position of the separator; and based on information about the position of the separator detected by the position detection device, A fuel remaining amount calculation device that detects the remaining amount of the liquid fuel stock solution contained in the fuel cell filling and recovering device.

In the above structure, the fuel cell filling and recovering device has a structure that moves toward the filling fuel storage space through the separator, and sprays the liquid fuel stock solution. Therefore, by detecting the position of the separator, the fuel cell can be detected. Fill the remaining amount of liquid fuel stock in the recoverer. The position of the partition can be detected by other components that detect the position of the partition.

The position detection device can be configured by a device capable of detecting the position of the separator without contacting the fuel cell filling recovery device.

In addition, the position detection device capable of non-contact detection can be composed of, for example, the following parts: a magnet provided on the separator; A detector that detects the position of the magnet through the magnetic field of the outer wall of the fuel cell filling recovery device.

In addition, it can have: a residual electric energy calculating device that calculates the electric energy that can be generated by the liquid fuel contained in the fuel cell filling and recovering device based on the information of the residual amount of the liquid fuel stock calculated by the fuel residual amount calculating device; and detecting; The electrical energy output from the fuel cell main body, based on the detected electrical energy, calculates the electrical energy output per unit time by a power consumption calculation device; the residual electrical energy calculation device calculated by the residual electrical energy calculation device can be generated by the power consumption The information of the power consumption per unit time calculated by the quantity calculating device calculates the remaining time information of the remaining time that can be generated by the liquid fuel stock contained in the fuel cell filling and recovering device. With this configuration, it is possible to know the remaining time information for generating electricity by the liquid fuel stock solution contained in the fuel cell filling and recovering device.

An eighth aspect of the present invention provides the fuel cell system according to any one of the fourth to seventh aspects, further comprising: storing the liquid fuel stock solution supplied from the fuel cell filling and recovering device and the fuel cell system supplied from the water supply port Fuel mixing tank for water.

According to the above configuration, since a tank for mixing and storing fuel and water supplied from the water supply port is provided, the water and the liquid fuel stock solution can be mixed in the tank, so that the concentration of the liquid fuel supplied to the anode can be easily controlled.

It should be noted that, in the structure, there is also a concentration detection device that detects the concentration of liquid fuel in the fuel mixing tank, and the first and second supply amounts are controlled based on the detection signal from the concentration detection device. Adjust the device so that the fuel concentration in the fuel mixing tank becomes a constant value.

In addition, by arranging at least the anode side of the fuel cell main body in the fuel mixing tank, the liquid fuel in the fuel mixing tank can be directly used on the anode side, so the pump for supplying liquid fuel from the tank to the anode can be omitted. It can be a simple structure.

A ninth aspect of the present invention provides the fuel cell system according to any one of the fourth to eighth aspects, wherein the diffusion layer arranged on the anode side is hydrophilic, and all the diffusion layers arranged on the cathode side are hydrophilic. The diffusion layer is hydrophobic.

According to this structure, the liquid fuel supplied to the anode can be diffused through the diffusion layer on the anode side having hydrophilicity, and can be quickly supplied to the electrolyte membrane. For example, even in the case where the supplied liquid fuel is only supplied to a part of the diffusion layer, due to the capillary phenomenon caused by the hydrophilicity of the diffusion layer or the action of gravity, the liquid fuel can be diffused while the The entire surface of the electrolyte membrane is uniformly and efficiently supplied. In addition, in the cathode, products generated by power generation, such as water, can be discharged through the diffusion layer on the side of the cathode having hydrophobicity. In addition, the discharge of this water can be efficiently discharged to the outside of the cathode because the diffusion layer has hydrophobicity. In addition, the hydrophobicity of the diffusion layer and the pressurization in the cathode by the air supply device have an effect of reducing the penetration of liquid fuel from the anode side through the electrolyte membrane.

Therefore, it is possible to provide a fuel cell system capable of efficiently supplying liquid fuel and efficiently discharging products in the main body of the fuel cell, and enabling efficient power generation. In addition, such high-efficiency power generation is possible without complicating the structure of the fuel cell system, and the fuel cell system can be made compact.

A tenth aspect of the present invention provides a regenerator for a fuel cell filling and recovering device, which is connected to the fuel cell filling and recovering device of the third aspect, and is used for a fuel cell filling and recovering device. The inside is divided into storage by a piston A fuel filling fuel supply part and an exhaust accommodating part, wherein a fuel filling connector connectable to the fuel replenishing connector of a fuel cell filling and recovering device is provided on the filling fuel supply part, and the effluent accommodating part Is provided with an exhaust recovery connector that can be connected to the water recovery connector of the fuel cell filling recovery unit; when the piston is moved to the filling fuel supply part side, the filling fuel supply part The fuel is supplied to the filling fuel storage space of the fuel cell filling and recovering device through the fuel replenishing connector, and at the same time, the exhaust material is collected into the filling and recovering space of the fuel cell filling and recovering device through the effluent recovery connector. The discharged material is recovered in the discharge storage part.

An eleventh aspect of the present invention provides a fuel cell system, including: --- a fuel cell main body having an anode for oxidizing fuel, a cathode for reducing oxygen, and being arranged between the anode and the cathode Between the electrolyte membrane, the hydrophilic anode-side diffusion layer arranged on the anode-side surface of the electrolyte membrane, and the hydrophobic cathode-side diffusion layer arranged on the cathode-side surface of the electrolyte membrane; - -A filling and recovering device for a fuel cell, the filling and recovering device for a fuel cell having: a filling fuel storage space capable of accommodating the liquid fuel stock solution supplied to the anode side, and a space for accommodating the exhaust generated in the cathode A container of the effluent recovery space; partitions configured to be movable in the axial direction inside the container and divide the interior of the container into the filling fuel storage space and the effluent recovery space; respectively In the container, a discharge inlet communicating with the discharge recovery space and used to take in discharges containing water and air from the cathode side of the fuel cell main body, and with the fuel The fuel accommodating space for filling of the battery body communicates and supplies the liquid fuel stock solution stored inside to the fuel supply port on the anode side of the fuel cell body; ---air for supplying air to the cathode Supply device.

Description of the drawings

The drawings are briefly described below.

These and other objects and features of the present invention will become clear based on the following description with reference to the accompanying drawings and preferred embodiments.

FIG. 1 is a schematic perspective view of a fuel cell stack as a fuel cell system according to each embodiment of the present invention when used as a battery for a notebook computer.

Fig. 2A is a perspective view showing an example of a method of coupling a fuel cell main body portion and a fuel discharge port of a fuel tank and an exhaust material supply port in the fuel cell system shown in Fig. 1.

2B is a perspective view showing another example of a method of combining the fuel cell main body part and the fuel discharge port of the fuel tank and the discharge material supply port.

Fig. 3 is a cross-sectional view showing a fuel container structure when the fitting method shown in Figs. 2A and 2B is adopted.

Fig. 4 is a perspective view illustrating the arrangement direction of the pressure release valve of the fuel tank for a fuel cell.

5A is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 1 of the present invention.

Fig. 5B is a diagram showing a modified example of the fuel cell filling and recovering device shown in Fig. 5A.

Fig. 6 is a diagram showing another modified example of the fuel cell filling and recovering device shown in Fig. 5A.

FIG. 7 is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 2 of the present invention.

FIG. 8 is a schematic diagram showing a state in which the fuel cell filling recovery device shown in FIG. 7 and the fuel cell filling recovery device used in the fuel cell filling recovery device are connected.

Fig. 9 is a diagram for explaining a leakage prevention mechanism included in the fuel cell filling and recovering device shown in Fig. 5A.

Fig. 10A is a cross-sectional view of the leakage prevention mechanism shown in Fig. 7.

Fig. 10B is a cross-sectional view of the plug part mated with the socket part shown in Fig. 10A.

Fig. 11 is a diagram showing a state in which the socket part shown in Fig. 10A and the plug part shown in Fig. 10B are engaged.

Fig. 12 is a diagram showing another modified example of the fuel cell filling and recovering device shown in Fig. 7.

Fig. 13 is a diagram showing a modification of the fuel cell system used in the fuel cell reclaimer shown in Fig. 12.

FIG. 14 is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 3 of the present invention.

Fig. 15 is a schematic diagram showing the structure of a gas-liquid separator used in the fuel cell system of Fig. 14.

16A is a schematic diagram showing the structure of a separator included in the fuel cell filling and recovering device used in the fuel cell system of FIG. 14.

Fig. 16B is a partial enlarged view of Fig. 16A.

FIG. 17A is a schematic diagram showing a separator structure included in the fuel cell filling and recovering device used in the fuel cell system of FIG. 14.

Fig. 17B is a cross-sectional view taken along the line AA' of Fig. 17A.

FIG. 18 is a schematic diagram showing a configuration of a modified example of the fuel cell filling and recovering device used in the fuel cell system of FIG. 14.

Fig. 19 is a schematic diagram showing the external structure of the fuel cell filling and recovering device of Fig. 18.

20 is a schematic diagram showing the structure of another modified example of the fuel cell filling and recovering device used in the fuel cell system of FIG. 14.

FIG. 21 is a schematic diagram showing the structure of another modification of the fuel cell filling and recovering device used in the fuel cell system of FIG. 14.

22 is a schematic diagram showing a state in which the fuel cell filling recovery device shown in FIG. 21 and the fuel cell filling recovery device used in the fuel cell filling recovery device are connected.

Fig. 23A is a schematic diagram showing the upper limit position of the separator of the fuel cell filling recovery device shown in Fig. 21.

FIG. 23B is a schematic diagram showing the lower limit position of the separator of the fuel cell filling and recovering device shown in FIG. 21.

FIG. 24 is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 4 of the present invention.

Fig. 25 is a schematic diagram showing the structure of a fuel cell main body used in the fuel cell system of Fig. 24.

Fig. 26A is a front view of the cathode side separator of the fuel cell main body of Fig. 25.

Fig. 26B is a cross-sectional view taken along line BB of Fig. 26A.

Fig. 27 is a schematic diagram showing the structure of the anode side separator of the fuel cell main body of Fig. 25.

FIG. 28 is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 5 of the present invention.

Fig. 29 is a schematic diagram showing the structure of a fuel cell reclaimer used in the fuel cell system of Fig. 28.

Fig. 30 is a partially enlarged cross-sectional view showing the separator structure of the fuel cell filling recovery device of Fig. 29.

Fig. 31 is a diagram showing the upper limit position and the lower limit position of the separator of the fuel cell filling recovery device of Fig. 29.

Fig. 32 is a block diagram showing the configuration of a control system used in the fuel cell system of Fig. 28.

FIG. 33 is a schematic configuration diagram showing the configuration of a fuel cell system according to Embodiment 6 of the present invention.

Fig. 34 is a diagram showing a schematic configuration of a fuel cell main body used in the fuel cell system of Fig. 33.

FIG. 35 is a schematic diagram showing the structure of a fuel cell filling and recovering device used in the fuel cell system of FIG. 33. FIG.

Fig. 36A is a schematic diagram showing the structure of the fuel cell filling recovery device of Fig. 35.

Fig. 36B is a cross-sectional view taken along the line BB' of Fig. 36A.

Fig. 37 is a schematic diagram of a state in which the fuel cell filling and recovering device of Fig. 35 is connected to the fuel cell filling and recovering device used in the fuel cell filling and recovering device.

Fig. 38 is an explanatory diagram showing a specific example of the material balance of the fuel cell system of Fig. 33.

39 is a graph showing the relationship between the amount of liquid fuel stock of the fuel cell of the fuel cell system of FIG. 33 and the total volume of water stored in the fuel tank and the total volume of water and fuel stored in the tank.

detailed description

Hereinafter, with reference to the accompanying drawings, a fuel cell filling and recovering device according to an embodiment of the present invention, a fuel cell system that can be connected to the fuel cell filling and recovering device, and a fuel cell filling and recovering device that perform regeneration of the fuel cell filling and recovering device will be described in detail. The regenerator is used. It should be noted that in each figure, the same components are given the same symbols.

The fuel cell system of each embodiment can be miniaturized in structure, so it is suitable for installation in a mobile device such as a mobile phone, and a small portable device such as a personal computer shown in FIG. 1. It should be noted that in FIG. 1, the symbol 10 represents the fuel cell system.

In addition, as described later, the fuel cell system of each of the above-described embodiments includes a fuel cell tank 20 for supplying fuel to the fuel cell main body. In the fuel cell system of each embodiment described above, in order to facilitate the loading and unloading of the fuel tank 20 for a fuel cell, as shown in FIGS. 2A and 2B, it is preferable to arrange the fuel tank 20 on one side of the fuel tank 20 for a fuel cell. The fuel discharge port 21 and the discharge recovery port 22 are connected. That is, the fuel discharge port 21 and the discharge recovery port 22 are located on one side, and only the fuel tank 20 for fuel cell is inserted into the part of the fuel cell main body 10 to complete the connection.

At this time, as will be described later, the pressure release valve 23 installed on the fuel tank is preferably arranged on a side different from the installation side of the fuel outlet 21 and the exhaust recovery port 22 except for the lower side parallel to the direction orthogonal to the direction of gravity. On the side.

It should be noted that, as described above, in the fuel tank 20 for a fuel cell shown in Figs. 2A and 2B where the fuel discharge port 21 and the effluent recovery port 22 are arranged on the same side surface, the fuel tank 20 for the fuel cell shown in FIGS. The space where the waste is recovered is the waste path 22a of the waste recovery space. As shown in FIG. 3, the discharge path 22a is formed by dividing the fuel cell fuel tank 20 with separators, or is formed by piping, or is formed by a guide rod with a hollow inside, and can adopt a structure that can be easily conceived by those skilled in the art. .

In addition, when the fuel cell system 10 is used as a power source of an instrument, the pressure release valve 23 of the fuel tank is preferably arranged in a direction other than the instrument side and the human body side. This is because the fuel cell main body of the fuel cell system reaches a temperature of approximately 60°C during power generation, so the gas discharged from the cathode is also approximately 60°C. Although the gas discharged from the pressure release valve 23 is slightly cooled, it is several tens of °C. In addition, the exhaust gas also contains water vapor. Therefore, if the pressure release valve 23 is located on the instrument side and the human body side, the instrument and the human body will be adversely affected due to the influence of heat and moisture. For example, as shown in FIG. 4, when the fuel cell system 10 is installed on a notebook computer, the user may put the computer on his lap to operate. Therefore, it is impossible to adopt a structure in which the pressure release valve 23 is arranged in the direction of gravity 310d. In addition, for the above reasons, it is also necessary to avoid being directed to the side of the computer. Therefore, at this time, it is preferable to orient the pressure release valve 23 in the upward direction 310a, the side direction 310b, and the back direction 310c.

Hereinafter, each embodiment of the fuel cell system of the present invention will be described.

First, the first embodiment of the present invention will be described. The fuel cell system 1010 of Embodiment 1 has the structure shown in FIG. 5A, and includes the fuel cell filling and recovering device 1020, and the fuel cell system main body 1001 to which the fuel cell filling and recovering device 1020 can be connected.

The fuel cell filling recovery device 1020 has a fuel filling mechanism 1060 that supplies the fuel 100 for filling to the fuel cell system main body 1001, and an exhaust recovery mechanism 1000 that recovers the exhaust generated by the fuel cell system 1010 from the fuel cell system 1010.

The fuel filling mechanism 1060 has: a filling fuel storage container 1040 that stores the filling fuel 100 and is connected to a fuel buffer tank 1030 of the fuel cell system 1010 through a pipe 1015; and is provided at the outlet of the filling fuel storage container 1040 Nearby leakage prevention mechanism 1025; for supplying the fuel 100 for filling from the fuel storage container 1040 for filling to the fuel buffer tank 1030, such as an electromagnetic filling fuel supply pump 1014. It should be noted that by providing the leakage prevention mechanism 1025, the filling fuel storage container 1040 can attach and detach the pipe 1015 connected to the fuel cell system 1010 or the filling fuel supply pump 1014.

The filling fuel storage container 1040 is filled with the filling fuel stock solution 100. As the filling fuel stock solution 100, organic solutions such as methanol and dimethyl ether are suitable examples, and methanol is particularly preferred. The material of the fuel storage container 1040 for filling needs to be able to circulate the fuel intact, so it needs a certain strength or more. For example, it can use polymer resins such as polyethylene terephthalate and polypropylene, glass or aluminum. , Stainless steel and other metals. From the viewpoint of reducing the frequency of replacement of the filling fuel storage container 1040 of the fuel cell filling recovery device 1020, the capacity of the filling fuel storage container 1040 is preferably much larger than the capacity of the fuel buffer tank 1030 of the fuel cell system 1010, for example, it has a number of Times to dozens of times the capacity. As an example, when the capacity of the fuel buffer tank 1030 is 50 ml, the capacity of the fuel storage container 1040 for filling is about 500 ml.

The leakage prevention mechanism 1025 is a mechanism that prevents the filling fuel 100 from leaking from the filling fuel storage container 1040 when the filling fuel storage container 1040 is not connected to the fuel cell system main body 1001. For example, the structure shown in FIG. 9 is taken as an example. The leakage prevention mechanism 1025 shown in FIG. 9 has a leakage prevention valve 1026 and a spring 1027 that are provided in the fuel storage container 1040 for filling. In contrast to the leakage prevention mechanism 1025, an ejector pin 1029 is provided on the pipe 1015 on the side of the fuel supply pump 1014 for filling. For the leakage prevention valve 1026 and the push pin 1029, high molecular resins such as polyethylene and polypropylene, and metals such as aluminum and stainless steel can be used.

In the leakage prevention mechanism 1025 configured in this way, when the filling fuel storage container 1040 is removed from the pipe 1015, the leakage prevention valve 1026 is in close contact with the connection port 1028 due to the contraction force of the spring 1027. Accordingly, leakage of the fuel 100 for filling is prevented. When the filling fuel storage container 1040 is connected to the pipe 1015, the ejection pin 1029 contacts the leakage prevention valve 1026, resists the contraction force of the spring 1027, and presses the leakage prevention valve 1026. Therefore, the leakage prevention valve 1026 is separated from the connection port 1028, and the filling fuel 100 in the filling fuel storage container 1040 can be supplied to the pipe 1015.

It should be pointed out that the structure of the leakage prevention mechanism 1025 is not limited to the structure shown in FIG. 9, and can adopt a disclosed structure or a structure conceivable by those skilled in the art.

The effluent recovery mechanism 1070 has: an effluent recovery container 1050 connected to the effluent buffer tank 1031 of the fuel cell system 1010 through a pipe 1017; a leakage prevention mechanism 1025 provided near the outlet of the effluent recovery container 1050; The discharge material 110 is supplied from the discharge material buffer tank 1031 to the discharge material recovery container 1050, for example, an electromagnetic discharge material recovery pump 1016. It should be noted that by providing the leakage prevention mechanism 1025, the effluent recovery container 1050 is detachable to the pipe 1017 connected to the fuel cell system main body 1001 or the effluent recovery pump 1016.

The effluent recovery container 1050 is a container for recovering the effluent, and can be made of the same material as the fuel storage container 1040 for filling of the fuel filling mechanism 1060 described above. In addition, the capacity of the effluent recovery container 1050 is preferably the same as the replacement frequency of the effluent recovery container 1050 from the viewpoint of making the replacement frequency of the filling fuel storage container 1040 of the fuel cell filling and recovering device 1020 and the replacement frequency of the effluent recovery container 1050 the same. The same capacity of the fuel storage container 1040 is used. In addition, the leakage prevention mechanism 1025 is the same as that of the fuel filling mechanism 1060 described above.

In addition, the filling fuel supply pump 1014 and the exhaust recovery pump 1016 are controlled by a control device 400 provided in the fuel cell filling and recovering 1020, in the fuel cell system 1001, or separately from them.

Next, the fuel cell system main body 1001 will be described.

As shown in FIG. 5A, the fuel cell system main body 1001 has a fuel cell main body 1000, and in this embodiment, it also has: a fuel buffer tank 1030, an exhaust buffer tank 1031, a fuel mixing tank 1032, a gas-liquid separation device 1033, and an installation The fuel connection portion 1034 at the supply port 1030a portion of the fuel buffer tank 1030 and the exhaust connection portion 1035 provided at the recovery port 1031a portion of the effluent buffer tank 1031. It should be noted that in the fuel cell system main body 1001, there are pumps in the fuel supply system path of the fuel cell main body 1000 and the exhaust discharge system path from the fuel cell main body 1000, but these pumps are not shown in the figure. And the description of its operation is omitted. In addition, the fuel buffer tank 1030 and the effluent buffer tank 1031 may be detachable from the fuel cell system main body 1001 separately or together.

The fuel cell main body 1000 includes a membrane electrode assembly 1002, an anode 1004, and a cathode 1006. A fuel circulation path 1036 is connected to the anode 1004, and an air supply path 1037 and an exhaust gas discharge path 1038 are connected to the cathode 1006.

The membrane electrode assembly 1002 has a solid polymer electrolyte membrane and is sandwiched by an anode 1004 and a cathode 1006. The anode 1004 is a structure in which a catalyst that decomposes fuel and extracts electrons, a fuel diffusion layer, and a separator as a current collector are laminated, and the cathode 1006 is a laminate of a proton and oxygen reaction catalyst, a diffusion layer of air, and a separator as the current collector.Structure. The structure. As the catalyst for the anode 1004 and the cathode 1006, platinum and ruthenium are used.

The cathode 1006 is connected to, for example, a motor-type air supply pump 1039, and the cathode 1006 is supplied with air or oxygen as a gas oxidant through an air supply path 1037 at a rate of 1 liter per minute, for example. In addition, the operation of the air supply pump 1039 is also controlled by the control device 400.

The fuel buffer tank 1030 contains the fuel 101 composed of the same liquid as the above-mentioned filling fuel 100, that is, an organic solution such as methanol and dimethyl ether, particularly methanol, and the discharge port 1030c is connected to the fuel mixing tank 1032. In addition, as described above, a fuel connection portion 1034 is provided in the supply port 1030a of the fuel buffer tank 1030, and the fuel connection portion 1034 is detachably connected to the filling fuel storage container 1040 of the fuel cell filling recovery unit 1020. Connected pipe 1015. In addition, the fuel connection portion 1034 has the same structure as the leakage prevention mechanism 1025 described with reference to FIG. 9, and when the pipe 1015 is not connected, the supply port 1030a of the fuel buffer tank 1030 is closed.

The supply port 1031b of the effluent buffer tank 1031 is connected to the effluent discharge path 1038 which is connected to the cathode 1006 and has a gas-liquid separation device 1033 on the way. While the fuel cell main body 1000 is generating electricity, air and water are discharged from the cathode 1006, but the air is separated by the gas-liquid separator 1033 and discharged to the outside. Therefore, the discharge buffer tank 1031 is supplied with the discharge 110 such as water and stored These discharges 110. In addition, the discharge port 1031 c of the discharge buffer tank 1031 is connected to the fuel mixing tank 1032. In addition, as described above, a connection part 1035 for discharge is provided in the recovery port 1031a of the discharge buffer tank 1031, and the discharge connection part 1035 is detachably connected to the discharge recovery container of the fuel cell filling recovery device 1020. 1050 is connected to the pipe 1017. In addition, the discharge connection portion 1035 has the same structure as the leakage prevention mechanism 1025 described with reference to FIG. 9, and the recovery port 1031 a of the discharge buffer tank 1031 is closed when the pipe 1017 is not connected.

As described above, to the fuel mixing tank 1032, the fuel 101 is supplied from the fuel buffer tank 1030, and water and the like of the discharge 110 are supplied from the discharge buffer tank 1031. Therefore, the fuel mixing tank 1032 contains the diluted fuel 120 diluted with the fuel 101. In addition, the fuel mixing tank 1032 is connected to the anode 1004 through a fuel circulation path 1036, and a gas-liquid separation device 1033 is provided in the middle of the recovery path from the anode 1004 to the fuel mixing tank 1032. During the power generation operation of the fuel cell main body 1000, the unreacted diluted fuel 120 and carbon dioxide are discharged from the anode 1004, but the carbon dioxide is separated by the gas-liquid separator 1033 and discharged to the outside, so the diluted fuel 120 is supplied to the fuel mixing tank 1031 .

Next, the filling and recovery operation of the fuel cell filling and recovering device 1020 when the fuel cell filling and recovering device 1020 having the above-mentioned structure is connected to the fuel cell system main body 1001 will be described. It should be noted that, before describing the filling and recovery operation, the operation of the fuel cell system 1010 having the above-mentioned structure will be described first.

The fuel 101 is supplied from the fuel buffer tank 1030 to the fuel mixing tank 1032, and the effluent 110 is supplied with water and the like from the fuel mixing tank 1032 from the effluent buffer tank 1031. The fuel 101 is diluted to a predetermined concentration of, for example, 2 mol of the diluted fuel 120. The diluted fuel 120 is supplied to the anode 1004. To the cathode 1006, an air supply pump 1039 is used to supply air or oxygen as an oxidant through an air supply path 1037. Therefore, the fuel cell main body 1000 uses carbon-supported precious metal catalysts such as Pt or Pt-Cu in the anode 1004 and the cathode 1006 to generate the above-mentioned reaction at the anode 1004 and the cathode 1006 to generate electricity.

The diluted fuel 120 passing through the anode 1004 and the carbon dioxide gas generated at the anode 1004 are separated from the carbon dioxide by the gas-liquid separator 1033 of the fuel circulation path 1036, and discharged to the outside, and the remaining diluted fuel 120 is circulated back to the fuel mixing tank 1032.

In addition, the gas passing through the cathode 1006 and the effluent 110 such as water generated at the cathode 1006 are separated by the gas-liquid separator 1033 through the effluent discharge path and discharged to the outside, and the remaining effluent 110 such as water is provided to the effluent buffer. Can 1031.

As the power generation progresses, the fuel 101 in the fuel buffer tank 1030 is consumed, and the discharges 110 such as water in the discharge buffer tank 1031 increase. Then, when the fuel 101 in the fuel buffer tank 1030 reaches a predetermined amount, for example, when there is almost no remaining amount, the above-mentioned filling and recovering operation by the fuel cell filling and recovering device 1020 is performed. It should be noted that, theoretically, as described above, three times the amount of water consumed by the anode 1004 is generated at the cathode 1006, but by appropriately setting the concentration of the diluted fuel 120 supplied to the anode 1004, for example, by setting it to 6.5 By weight%, the sum of the fuel and water consumed can be almost the same as the water produced.

Next, the filling recovery operation will be described.

Connect the pipe 1015 connected to the filling fuel storage container 1040 of the fuel cell recharger 1020 and the pipe 1017 connected to the exhaust recovery container 1050 to the fuel of the fuel buffer tank 1030 of the fuel cell system main body 1001. The part 1034 and the discharge of the discharge buffer tank 1031 are connected by a connection part 1035.

It should be pointed out that the pipe 1015 and the pipe 1017 can be installed in the fuel cell filling recovery unit 1020 together with the pumps 1014 and 1016 as in the present embodiment, or can be provided as another independent component. In addition, they can be installed in The fuel cell system main body 1001.

In addition, the pipe 1015 and the pipe 1017 can be connected separately, but from the standpoint of convenience and operability, it is preferable that the structure is installed on the fuel cell filling and recovering device 1020, and the fuel cell filling and recovering device 1020 is connected to the When connecting to the fuel cell system main body 1001, both are connected to the fuel connection portion 1034 and the exhaust connection portion 1035 at the same time. Specifically, as shown in FIG. 3 described above, it is preferable to arrange a pipe 1015 communicating with the fuel discharge port 21 and a pipe 1017 communicating with the exhaust supply port 22 on the same side surface.

After the connection, the filling fuel supply pump 1014 is operated, and the filling fuel 100 contained in the filling fuel storage container 1040 is supplied into the fuel buffer tank 1030 through the pipe 1015 and the fuel connection portion 1034. In addition, in order to shorten the working time, it is preferable to operate the exhaust recovery pump 1016 in parallel with the supply operation of the filling fuel 100 to pass the exhaust 110 such as water contained in the exhaust buffer tank 1031 through the exhaust connection 1035 and The pipe 1017 returns to the effluent recovery container 1050. At this time, in the effluent buffer tank 1031, in order to dilute the fuel, it is preferable that the effluent 110 such as a small amount of water remains.

When the supply of the filling fuel 100 and the recovery of the exhaust 110 are completed, stop the filling fuel supply pump 1014 and the exhaust recovery pump 1016, and then remove them from the fuel connection 1034 and the exhaust connection 1035, respectively The pipe 1015 and the pipe 1017 complete the filling and recovery operation.

As described above, by having the fuel cell filling and recovering device 1020 that can be freely attached to and detached from the fuel cell system main body 1001, fuel is automatically supplied from the filling fuel storage container 1040 to the fuel buffer tank 1030 through the pipe 1015, so the fuel will not be spilled. It is external and can be completely supplied with fuel, and the effluent 110 stored in the effluent buffer tank 1031 can be automatically recovered from the effluent buffer tank 1031 to the effluent recovery container 1050 through the pipe 1017. According to this, it is possible to prevent water vapor and the like from being discharged from the fuel cell system 1010 to the outside.

In addition, a leak prevention mechanism 1025 is provided in the fuel cell filling recovery unit 1020. By making it have a larger capacity than the fuel buffer tank 1030, it is possible to prevent fuel leakage when the fuel buffer tank 1030 is connected, and to reduce the amount of fuel for filling. The frequency of replacement of the container 1040.

It should be noted that, in the above-mentioned first embodiment, the fuel cell filling and recovering device 1020 has two independent containers, such as a filling fuel storage container 1040 and an effluent recovery container 1050. However, as shown in FIG. 5B, it can also be used One container has the functions of a filling fuel storage container 1040 and an effluent recovery container 1050. That is, as described above, by supplying the fuel 100 for filling to the fuel buffer tank 1030, the container 1051 accommodating the fuel 100 for filling becomes empty, so that the container 1051 can be used for the recovery of the effluent 110 after the fuel is supplied. It should be noted that when a container is used in this way, as shown in FIG. 5B, it is preferable to provide a discriminating tool 1052 for judging the contents of the container 1051. For example, in the discharge 110 from the cathode 1006, as a by-product, formic acid is contained. Therefore, the determination tool 1052 can use a test tool that changes the color and the nature of the liquid according to the content. As a test tool, for example, a test tool for measuring the pH of the liquid can be used. pH test paper.

In addition, as a modified example, it is possible to use one container in appearance that forms the fuel storage space for filling and the discharge recovery space.

By using the same container 1241 as the filling fuel storage container and the effluent recovery container in this way, the circulation of the filling fuel storage container can be improved, and the cost can be reduced.

In the above-mentioned modification of FIG. 5B, two fuel supply pumps 1114 for filling and a pump 1116 for effluent recovery are provided. However, as shown in the other modification of FIG. 6, the fuel cell filling and recovering device 1220 is passed In the pipe 1215 or the pipe 1217, a switching valve 1209 for switching the flow path is provided, which can be a pump 1213, and in addition, a container 1241 can be used. It should be noted that in FIG. 6, the control device 402 corresponds to the above-mentioned control device 401 and controls the operations of the pump 1213, the switching valve 1209, and the air supply pump 1239.

In addition, in FIG. 6, as in FIG. 5A, the fuel cell filling recovery device 1220 has a pipe 1215 or a pipe 1217 structure as an example, but the fuel cell system main body 1201 may be provided with a pump 1213 and a switching valve 1209, Or the structure of the switching valve 1209. According to this structure, the connection part between the fuel cell recharger 1220 and the fuel cell system main body 1201 can be made at one place.

Next, the second embodiment of the present invention will be described.

FIG. 7 shows a fuel cell filling recovery device 1320 according to the second embodiment. The fuel cell filling and recovering device 1320 has a hollow filling and recovering container 1340; it is disposed in the filling and recovering container 1340, can move along the axial direction 1340a of the filling and recovering container 1340, and divides the filling and recovering container 1340 into discharge The partition 1350 of the material recovery space 1341 and the filling fuel storage space 1342; the leakage prevention mechanism 1325 as the connection part that is attachable and detachable to the above-mentioned pipes 1315 and 1517.

As the separator 1350, for example, polymer resins such as polyethylene terephthalate, polycarbonate, and Teflon (trade name), or glass, or metals such as aluminum and stainless steel can be used. When the thickness of the separator 1350 is thin, the initial filling fuel occupancy rate in the filling recovery unit 1340 increases, which is good, but if it is too thin, the strength during pressurization is insufficient. Therefore, depending on the material and size of the separator 1350, the required plate thickness varies.

In addition, the contact portion 1350a of the partition 1350 with the inner surface 1340b of the filling and recovery container 1340 is provided with, for example, an O ring made of an elastic material or a sealing member 1351 of the shape shown in FIG. 7 so as to be accommodated in the discharge recovery space 1341. The effluent in the battery does not mix with the fuel for filling contained in the fuel storage space 1342 for filling.

In addition, a guide member for guiding the movement of the partition 1350 along the axial direction 1340a can also be provided in the filling recovery container 1340. As the guide member, consider the rod 1343 provided through the partition 1350 along the axial direction 1340a, and a recess or a recess formed on the inner surface 1340b of the filling and recovery container 1340 along the axial direction 1340a and fitted with the partition 1350. Convex and so on. It should be noted that when the rod 1343 is used, a sealing member such as an O ring is provided in the penetrating portion of the partition 1350 to prevent leakage of the discharge and filling fuel at the penetrating portion.

As an example, the leakage prevention mechanism 1325 can use a commercially available socket part shown in FIG. 10A. The socket portion 1325 includes a plug insertion recess 1326, a valve portion 1327, and a spring 1329 for pressing the valve portion 1327 against the valve seat portion 1328. In addition, in the valve portion 1327, a sealing member such as a gasket is provided at the contact portion with the valve seat portion 1328. Normally, the valve portion 1327 is pressed against the valve seat portion 1328 by a spring 1329 to prevent the filling fuel and discharge from being filled. The inside of the recovery container 1340 leaks to the outside.

Opposite to the socket part 1325, a commercially available plug part 1335 is provided on the pipe 1315 and the pipe 1317. The plug portion 1335, for example, as shown in FIG. 10B, can be connected to the socket portion 1325, and has a convex portion 1336 that fits with the plug insertion recess 1326 of the socket portion 1325, a valve portion 1337, and a valve portion 1337 that presses the valve portion 1337 on the valve seat portion 1338. The spring 1339. By fitting the plug portion 1335 with the plug insertion recess 1326 of the socket portion 1325, as shown in FIG. 11, the valve portion 1327 and the valve portion 1337 are in contact with each other, and the valve portions 1327, 1337 and the valve seat portions 1328, 1338 are respectively released. Contact, the exhaust recovery space 1341 and the pipe 1317 are opened, and the filling fuel storage space 1342 and the pipe 1315 are opened. In addition, an O ring 1332 for preventing leakage is provided in the plug insertion recess 1326 to prevent liquid from leaking from the connection portion when the socket portion 1325 and the plug portion 1335 are connected.

Next, description will be given of the filling and recovering operation of the fuel cell filling and recovering device 1320 when the fuel cell filling and recovering device 1320 of the second embodiment having the above-mentioned configuration is connected to the fuel cell system main body 1301. It should be noted that in the initial state, the fuel cell filling and recovering device 1320 is filled with the filling fuel 100. According to this, the separator 1350 is located on the pipe 1317 side in the filling and recovering container 1340, that is, on the right side of the figure. .

As described above, the fuel cell filling recovery device 1320 is connected to the fuel cell system main body 1301 by connecting the pipe 1315 and the pipe 1317 to the fuel buffer tank 1330 and the exhaust buffer tank 1331 of the fuel cell system main body 1301. Furthermore, as described in the first embodiment, by the power generation operation, the effluent 110 such as water is stored in the effluent buffer tank 1331, and the fuel 101 is consumed from the fuel buffer tank 1330. According to this, the pump 1314 for effluent recovery is properly operated, and the effluent 110 in the effluent buffer tank 1331 is supplied to the effluent recovery space 1341 of the fuel cell filling recovery unit 1320 through the pipe 1317. By this supply operation, the pressure in the exhaust recovery space 1341 rises, the partition 1350 is pressed, and the partition 1350 moves to the side of the filling fuel storage space 1342 along the axial direction 1340a, that is, to the left in the figure. By the movement of the separator 1350, the filling fuel 100 contained in the filling fuel storage space 1342 is pressurized and supplied to the fuel buffer tank 1330 of the fuel cell system main body 1301 through the pipe 1315. That is, the pump 1314 for discharge recovery functions as a pressure difference generating mechanism.

The above-mentioned actions are repeated, and the filling and recovery action is performed until the filling fuel 100 contained in the filling fuel storage space 1342 is almost or completely empty. It should be noted that in a state where the filling fuel 100 is completely absent, the filling recovery unit 1320 for the fuel cell is filled with the exhaust material 100.

As described above, according to the fuel cell filling and recovering device 1320, the effect of the fuel cell filling and recovering device 1020 of the first embodiment described above can be produced, that is, it does not spill the fuel to the outside, and the fuel is supplied safely, and the fuel can be automatically recovered and discharged. In addition, in the filling recovery container 1340 as one container, the recovery of the effluent 110 from the effluent buffer tank 1331 of the fuel cell system main body 1301 and the supply of the fuel for filling to the fuel buffer tank 1330 can be performed at the same time. 100 actions.

In addition, because it is composed of a single-tank filling and recovery container 1340, by connecting the fuel cell filling and recovering device 1320 to the fuel cell system main body 1301, the fuel buffer tank 1330 and the effluent buffer tank 1331 can be connected at one time. , Handling during loading and unloading becomes very easy.

It should be noted that by the action of recovering the effluent 110 in the fuel cell filling and recovering device 1320, the separator 1350 is pressed to pressurize the filling fuel 100 in the fuel cell filling and recovering device 1320, so it is not necessary to install the filling Fuel supply pump 1314. Accordingly, as described above, the unit structure can be simplified by cooperating with the singularization of the container.

In addition, in the above description, the exhaust recovery pump 1316 is operated first, but the filling fuel supply pump 1314 may be operated first. By the operation of the filling fuel supply pump 1314, the filling fuel 100 in the filling fuel storage space 1342 is reduced, and accordingly, the diaphragm 1350 moves to the left in the figure along the axial direction 1340a. Accordingly, the exhaust material recovery space 1341 becomes negative pressure, and the exhaust material 110 is sucked from the exhaust material buffer tank 1331 into the exhaust material recovery space 1341. In this case, it is not necessary to provide the pump 1316 for waste recovery. That is, at this time, the filling fuel supply pump 1314 becomes a pressure difference generating mechanism.

In addition, in the above-mentioned first and second embodiments, the filling fuel supply pump 1314 and the exhaust recovery pump 1316 are provided on the fuel cell filling and recovering devices 1020 to 1320, but they are not limited to this structure and may be provided. On the fuel cell system main body 1001 to 1301.

In addition, as a modification of the fuel cell filling and recovering device 1320 of the second embodiment described above, the fuel cell filling and recovering device 1420 shown in FIG. 12 can be configured. In the second embodiment described above, the separator 1350 is moved by the operation of the filling fuel supply pump 1314 or the exhaust recovery pump 1316. However, in the fuel cell filling and recovering device 1420 of the modified example, the piston 1455 is used to make it move. The movement eliminates the structure of the fuel supply pump for filling and the pump for effluent recovery. The other structure is the same as the structure of the fuel cell reclaimer 1320, so the description is omitted here.

The piston 1455 has a partition 1456; a rod 1457 protrudingly provided on the partition 1456, extending along the axial direction 1440a, passing through the filling and recovering container 1420 to the outside. In addition, the sealing member 1451 is provided in the contact portion of the partition 1456 with the inner surface 1440b of the filling and recovering container 1420. In addition, the through portion of the rod 1457 of the filling and recovering device 1420 is also provided with an unillustrated device for preventing leakage. Sealing member.

In the filling and recovering device 1420 for the fuel cell, in the initial state, the filling fuel storage space 1442 is filled with the filling fuel 100, and the piston 1445 is located on the pipe 1417 side, that is, on the right side of the figure. At the time of fuel filling, the fuel cell system main body 1401 is connected to the fuel cell system main body 1401 by connecting the pipe 1415 and the pipe 1417 to the fuel cell system main body 1401 by connecting the pipe 1415 and the pipe 1417 to the fuel cell system main body 1401. After the connection, the piston 1455 is pressed toward the pipe 1415 side along the axial direction 1440a. By pressing the piston 1455, the filling fuel 100 contained in the filling fuel storage space 1442 is pressurized, and the filling fuel 100 is supplied into the fuel buffer tank 1430 through the pipe 1415. The discharge recovery space 1441 generates negative pressure due to the movement of the piston 1455. Due to the negative pressure generated in the effluent recovery space 1441, the effluent 110 in the effluent recovery container 1431 is sucked into the effluent recovery space 1441 through the pipe 1417. That is, in the above-described embodiment, the piston 1455 functions as a pressure difference generating mechanism.

As described above, according to the fuel cell filling and recovering device 1420, the same effect as the above-mentioned effect produced by the fuel cell filling and recovering device 1320 of the second embodiment can be produced by one movement of the piston 1455 described above. According to the fuel cell filling recovery device 1420, by using the piston 1455, the filling fuel supply pump and the exhaust recovery pump are not required. Accordingly, the fuel cell filling and recovering device 1420 can further simplify the device structure compared to the fuel cell filling and recovering device 1320.

It should be pointed out that the movement of the piston 1455 can be performed mechanically using a drive source such as a motor, or manually. In particular, by manually operating the piston 1455, a simple device structure can be obtained.

In addition, when the fuel cell filling recovery device 1420 is used, it can be connected to the fuel cell system 1403 shown in FIG. 13. In the fuel cell system 1401 of FIG. 12, a structure in which the fuel buffer tank 1330 and the exhaust buffer tank 1431 are separately provided is adopted, but in the fuel cell system 1403 of FIG. 13, as shown in the figure, it has an integrated fuel exhaust Can 1480. It should be noted that the other structure of the fuel cell system 1403 is the same as the structure of the fuel cell system 1401, and the description here is omitted. In addition, the fuel discharge tank 1480 may adopt a structure that can be removed from the fuel cell system 1403.

The fuel discharge tank 1480 has a partition 1483 inside the fuel discharge tank 1480 that can move along the axial direction 1480a of the fuel discharge tank 1480. The partition 1483 divides the inside of the fuel discharge tank 1480 into a fuel portion 1481 and a dischargeThings Department1482. It should be noted that a sealing member provided on the separator 14510 of the fuel cell filling and recovering device 1420 is provided at the contact portion of the separator 1483 with the inner surface of the fuel discharge container 1480. The fuel part 1481 is a part that contains the fuel 101, is connected to the fuel mixing tank 1432 of the fuel cell system main body 1403, and is detachably connected to the filling fuel storage space 1442 of the fuel cell filling recovery unit 1420 through a pipe 1415 . The exhaust part 1482 is a part that contains the exhaust 110, is connected to the fuel mixing tank 1432 of the fuel cell system main body 1403, and is detachably connected to the exhaust recovery space 1441 of the fuel cell filling and recovering device 1420 through a pipe 1417. connection.

In the fuel cell system 1403 configured in this way, the fuel 101 in the fuel section 1481 is supplied to the anode 1404 by the power generation of the fuel cell main body 1400, and the exhaust 110 is recovered from the cathode 1406 to the discharge section 1482. Due to the consumption of the fuel 101 and the recovery of the exhaust 110, the partition 1483 moves to the fuel portion 1481 side along the axial direction 1480a.

When the fuel 100 is filled and the exhaust 110 is recovered, the fuel cell filling and recovering device 1420 is connected to the fuel exhaust tank 1480 of the fuel cell system main body 1403. As described above, the fuel cell filling and recovering device 1420 is The piston 1455 presses the pipe 1415 on the left side of the figure, pressurizes the filling fuel 100 contained in the filling fuel storage space 1442, and supplies it to the fuel portion 1481 of the fuel discharge tank 1480 through the pipe 1415. By this fuel supply operation, the fuel 101 in the fuel portion 1481 presses the partition 1483 of the fuel discharge tank 1480 in the axial direction 1480b. According to this, the separator 1483 pressurizes the discharge 110 in the discharge portion 1482 of the fuel discharge tank 1480 and sends it to the discharge recovery space 1441 of the fuel cell filling recovery unit 1420 through the pipe 1417.

By combining the fuel cell filling and recovering device 1420 and the fuel cell system 1403 in this way, when the fuel is filled and the discharged material is recovered, the fuel discharge tank 1480 and the fuel cell filling and recovering device 1420 are connected, and one of the pistons 1455 is pressed. The operation can efficiently carry out fuel filling and exhaust recovery at the same time. In addition, pumps for fuel filling and exhaust recovery are not required, and the device structure can be simplified. In particular, by making the movement of the piston 1455 manual, the fuel cell filling and recovering device 1420 does not require electric power, and the structure of the device can be further simplified.

As described above, in the second embodiment, the fuel cell filling and recovering device 1320 after the filling fuel 100 is supplied to the fuel cell system main body 1301 is refilled with the filling fuel 100 and recovered in the exhaust recovery space 1341. For the recovery of the effluent 110, the regenerator connected to the fuel cell filling recovery unit 1320 will be described below.

The regenerator 3300 shown in FIG. 8 has a hollow regenerator housing 3310 of the same size as the above-mentioned fuel cell filling and recovering regenerator 1320; it is disposed in the regenerator housing 3310 and can be along the axial direction of the regenerator housing 3310. Piston 3320 moved by 3310a; the above-mentioned plug parts 3336 and 3335 respectively matched with socket parts 1325 and 1325 provided at two places in the fuel cell filling and recovering device 1320.

The piston 3320 has a partition 3321 that divides the interior of the regenerator housing 3310 into an exhaust accommodating portion 3311 and a fuel supply portion 3312; the partition 3321 is protrudingly provided on the partition 3321, extends in the axial direction 3310a, and penetrates the regenerator housing 3310, reach the outside pole 3322. In addition, a contact portion 3321a of the partition 3321 with the inner surface 3310b of the regenerator housing 3310 is provided to prevent the exhaust 110 contained in the exhaust storage portion 3311 from mixing with the filling fuel 102 contained in the filling fuel supply portion 3312. There are sealing members (not shown) such as the above-mentioned O ring. In addition, a sealing member for preventing leakage is also provided at the portion where the rod 3322 penetrates the regenerator housing 3310.

As the material of such a piston 3320, polymer resins such as polyethylene, polypropylene, and Teflon (trade name) are preferable.

In addition, a guide member for guiding the movement of the piston 3320 along the axial direction 3310a can also be provided in the regenerator housing 3310. As the guide member, it is considered that a rod 3313 is provided through the partition 3321 along the axial direction 3310a; or is formed on the inner surface 3310b of the regenerator housing 3310 along the axial direction 3310a, and a concave portion or a recess that fits the partition 3321 Convex and so on.

Next, the regeneration operation of the fuel cell filling recovery unit 1320 using the regenerator 3300 having the above structure will be described. It should be noted that the regenerator 3300 is in a state of being fully charged with the fuel 102 for filling, and the regenerator 1320 for the fuel cell is in a state of being filled with the exhaust material 110 to some extent or completely.

As shown in FIG. 8, the socket part 1325 of the discharge recovery space 1341 of the fuel cell filling recovery unit 1320 and the plug part 3336 of the discharge housing part 3311 of the regenerator 3300 are connected, and the fuel cell filling recovery unit 1320 The socket part 1325 of the fuel storage space 1342 for filling and the plug part 3335 of the filling fuel supply part 3312 of the regenerator 3300 are connected. According to this, the exhaust material recovery space 1341 and the exhaust material storage portion 3311 communicate, and the filling fuel storage space 1342 and the filling fuel supply portion 3312 communicate. It should be pointed out that Figure 8 shows before the regeneration operation.

Next, the operator presses the rod 3322 of the piston 3320 in the axial direction 3310a. By pressing the piston 3320 to the side of the filling fuel supply part 3312, the filling fuel 102 contained in the filling fuel supply part 3312 of the regenerator 3300 is supplied to the fuel cell filling recovery unit 1320 through the socket part 1325 and the plug part 3335. Use fuel storage space 1342. By supplying the filling fuel 102 to the filling fuel storage space 1342 , the separator 1350 of the fuel cell filling recovery device 1320 presses the exhaust material 110 in the exhaust material recovery space 1341. According to this, the discharge 110 is supplied to the discharge accommodating part 3311 of the regenerator 3300 through the socket part 1325 and the plug part 3336. In this way, the filling fuel 102 fills the fuel cell filling recoverer 1320, and the effluent 110 fills the regenerator 3300.

It should be noted that even if there is residual fuel in the filling fuel storage space 1342 of the fuel cell filling and recovering device 1320, the above-mentioned regeneration operation can be performed without any problem. In addition, even if it is contained in the filling fuel supply section 3312 of the regenerator 3300 The amount of the fuel 102 for filling in is smaller than the capacity of the fuel accommodating space 1342 for filling, and it can be performed without any problem. In the latter case, the discharge of the discharge material 110 from the discharge material recovery space 1341 of the fuel cell filling recovery unit 1320 is completed midway, but it does not impede the operation of the fuel cell system main body 1301.

Next, Embodiment 3 of the present invention will be described.

FIG. 14 is a schematic configuration diagram showing a schematic configuration of a fuel cell system 1510 according to Embodiment 3 of the present invention.

As shown in FIG. 14, the fuel cell system 1510 has: a fuel cell main body 1500 that converts the chemical energy of the fuel into electrical energy by electrochemical conversion to generate electricity; and supplies the fuel cell main body 1500, which is necessary for the power generation, to the fuel cell main body 1500. Auxiliary system. In addition, the fuel cell system 1510 is a direct methanol fuel cell (DMFC) that uses methanol aqueous solution as an example of organic liquid fuel as fuel, and directly extracts protons from the methanol to generate electricity.

As shown in FIG. 14, the fuel cell main body 1500 has: an anode (fuel electrode) 1504, a cathode (air electrode) 1506, a membrane electrode assembly 1502 arranged between the anode 1504 and the cathode 1506, as the membrane electrode assemblies respectively arranged The diffusion layers on the surface of the electrolyte membrane of 1502 are anode-side diffusion layer 1507 and cathode-side diffusion layer 1508. The anode 1504 has a function of oxidizing the supplied methanol to perform a reaction (anode reaction) for extracting protons and electrons. The electrons move to the cathode 1506 through an unshown external circuit (power generation circuit) that electrically connects the anode 1504 and the cathode 1506, and the protons move to the cathode 1506 through the membrane electrode assembly 1502. In addition, the cathode 1506 uses oxygen supplied from the outside, protons moved from the anode 1504 through the membrane electrode assembly 1502, and electrons flowing through the external circuit to undergo a reduction reaction to produce water (cathode reaction). Function. In this way, the oxidation reaction proceeds at the anode 1504 and the reduction reaction proceeds at the cathode 1506, allowing electrons to flow to the external circuit, generating electric current, and generating power.

Specifically, as the membrane electrode assembly 1502, for example, a membrane electrode assembly whose permeation of liquid fuel is 1/10 of the conventional one is used. The membrane electrode assembly 1502 is formed on one surface as the anode catalyst of the anode 1504, formed by dispersing platinum and ruthenium or an alloy of platinum and ruthenium on a carbon-based powder carrier, and on the other surface as the cathode 1506 The cathode catalyst is formed by dispersing and supporting platinum particles on a carbon-based carrier. The whole of the catalyst formed in the membrane electrode assembly 1502 is referred to as a membrane electrode assembly. The diffusion layer 1507 on the anode side is formed by, for example, hydrophilizing carbon paper, and the diffusion layer 1508 on the cathode side is formed by hydrophobizing carbon paper, for example. It should be pointed out that such hydrophilic treatment can improve the hydrophilicity by activating the carbon paper with water vapor. In addition, the hydrophobic treatment involves impregnating carbon paper with a dispersion of a fluorine resin such as polytetrafluoroethylene to impart hydrophobicity. After the diffusion layers 1507 and 1508 are in close contact with the surface of the electrolyte membrane of the membrane electrode assembly, they are fixed to the case with a separator interposed therebetween to form a fuel cell main body 1500. In addition, the diffusion layers 1507 and 1508 can also be used as electrodes.

It should be noted that, for the diffusion layers 1507 and 1508, instead of using the carbon paper, carbon cloth can also be used. As the membrane electrode assembly 1502, for example, three sheets of Nafion (trade name) of DuPont Co., Ltd. are overlapped to reduce permeation. In addition, as the membrane electrode assembly 1502, for example, a porous membrane having submicron-order pores may be filled with a pore-filled electrolyte membrane filled with an electrolyte polymer, or a ceramic porous body may be filled with an electrolyte polymer.

In addition, as shown in FIG. 14, the anode 1504 has a fuel supply port 1509 for supplying a methanol aqueous solution to the inside in order to carry out the anode reaction. The fuel supply port 1509 is provided with a device for discharging carbon dioxide generated by the anode reaction. Exhaust valve 1511.

In addition, the cathode 1506 has an air supply port 1512 for supplying oxygen used in the implementation of the anode reaction, for example, air is used to supply the air to the inside; and for discharging water generated in the cathode reaction from the inside (including Any state of liquid or gaseous state or a state in which each state is mixed) discharge port 1513.

It should be noted that the effluent contains water as the main component, but in addition to it, it sometimes also contains formic acid, methyl formate, and methanol (by permeation described later).

Next, the structure of the auxiliary machine system of the fuel cell system 1510 will be described. As the structure of the auxiliary equipment system, there are an auxiliary equipment structure for supplying methanol aqueous solution to the anode 1504 of the fuel cell main body 1500, an auxiliary equipment structure for supplying air to the cathode 1506, and an auxiliary equipment structure for recovering exhaust generated by the cathode 1506. The auxiliary machinery structure of the thing that is water.

First, as shown in FIG. 14, as an auxiliary structure for the fuel supply, there are: a fuel cell filling recovery unit 1520 that accommodates and can supply a methanol aqueous solution as a liquid fuel to the anode 1504; and is connected to a fuel cell filling recovery unit 1520 The fuel supply line 1536 of the fuel supply port 1509 of the fuel supply port 1509 of the fuel supply port 1520 and the anode 1504.

The fuel cell filling and recovering device 1520 has a filling fuel storage space 1542 that contains a liquid fuel stock solution in its inner space, and an exhaust recovery space 1541 that mainly recovers water as the exhaust generated by the cathode 1506. In addition, the fuel cell filling and recovering device 1520 has a partition 1550 that can move freely along its inner wall, and divides the inner space into a filling fuel storage space 1542 and an effluent recovery space 1541. That is, in the fuel cell filling and recovering device 1520, the separator 1550 moves, and the volume of the filling fuel storage space 1542 and the volume of the exhaust material recovery space 1541 can be changed by moving the divided positions. It should be noted that the total volume of the filling fuel storage space 1542 and the exhaust recovery space 1541 becomes the volume of the fuel cell filling recovery unit 1520, so when the filling fuel storage space 1542 and the exhaust recovery space 1541 are When the volume of one side increases, the volume of the other side decreases according to the increased volume part.

In addition, one end of the fuel supply pipe 1536 is connected to the filling fuel storage space 1542, and the liquid fuel stock solution contained in the filling fuel storage space 1542 can be supplied to the anode 1504 from the fuel supply port 1509 through the fuel supply pipe 1536. In addition, an adjustment valve 1560 capable of adjusting the supply amount (flow rate) of the liquid fuel stock solution supplied through the fuel supply line 1536 is provided in the middle of the fuel supply line 1536. It should be noted that the adjustment valve 1560 can close the fuel supply pipe 1536 communicating with the filling fuel storage space 1542 by closing the opening degree. In addition, in the filling fuel storage space 1542 of the fuel cell filling recovery unit 1520, for example, in the initial state, a methanol aqueous solution having a concentration of 63.8 wt% by weight is contained as a liquid fuel stock solution.

As an auxiliary machine structure for supplying the air, there is an air supply line 1537 connected to one end of the air supply port 1512 of the cathode 1506; it is arranged in the middle of the air supply line 1537, and is connected to the air supply line 1537 through the air supply line 1537. An air supply pump 1539 for supplying air in the cathode 1506. As the air supply pump 1539, it is preferable to use a small size and low power consumption, for example, a motor pump (with a check valve, discharge volume: 0 to 2L/min, discharge pressure: 30kPa). When used, for example, 1L/min supply air. In addition, when power generation is performed by the fuel cell main body 1500, the air supply pump 1539 is driven to supply necessary air (or oxygen) into the cathode 1506, and when the power generation is stopped, the driving of the air supply pump 1539 is stopped.

In addition, as an auxiliary machine structure for recovering the water, there is a discharge port 1513 communicating with the cathode 1506 and an effluent recovery space 1541 of the fuel cell filling recovery unit 1520, and the water generated by the cathode 1506 is supplied to the effluent. The water recovery line 1538 of the recovery space 1541.

In the cathode 1506, an exhaust whose main component is water is generated by power generation, but the inside of the cathode 1506 is supplied with air by an air supply pump 1539. Therefore, the mixture of the exhaust and air (for example, a gas-liquid mixture) is transported from the cathode 1506 to the water recovery line 1538 through the discharge port 1513. In addition, the resulting water is often contained in the mixture in the form of water vapor. Therefore, the gas-liquid mixture is separated into gas and liquid, and the gas-liquid separator 1533 that sends the liquid to the water recovery line 1538 is provided in the middle of the water recovery line 1538. In addition, the water recovery line 1538 between the gas-liquid separator 1533 and the fuel cell filling recovery unit 1520 is provided with a valve 1561 for closing the water recovery line 1538 to the effluent recovery space 1541.

Here, FIG. 15 shows a schematic diagram of the schematic structure of the gas-liquid separator 1533. As shown in FIG. 15, the gas-liquid separator 1533 has a gas-liquid separation chamber 1533a that is stored in a state where the water 110 of the effluent discharged from the cathode is separated to the bottom and the gas 112 is separated to the top; The end of the water recovery pipe 1538 of the cathode 1506 is an introduction pipe 1521 arranged below the space in the gas-liquid separation chamber 1533a; it communicates with the space above the gas-liquid separation chamber 1533a to discharge excess gas contained in the space , A pressure regulating valve 1562 that adjusts the space to a given pressure; a water discharge port 1522 located near the bottom of the gas-liquid separation chamber 1533a.

In addition, as shown in FIG. 15, the introduction pipe 1521 is arranged to be immersed in the water contained in the gas-liquid separation chamber 1533a. In addition, in order to increase the contact area between the water and the outer surface of the introduction pipe 1512, for example, it has a spiral shape. shape. The introduction pipe 1521 has such a configuration and shape that when the mixture of water and air sent through the water recovery pipeline 1538 passes through the introduction pipe 1521, it performs efficient heat exchange with the surrounding water, condenses, and introduces it in a liquefied state. In the gas-liquid separation chamber 1533a. In addition, the gas remaining in the mixture moves above the gas-liquid separation chamber 1533a. However, by providing a water discharge port 1522 near the bottom of the gas-liquid separation chamber 1533a, the water 110 in the lower part of the chamber can be discharged through the water discharge port 1522 without causing the gas 112 in the upper part of the chamber to flow out. It should be noted that the water discharged through the water discharge port 1522 is contained in the discharge recovery space 1541 of the fuel cell filling recovery unit 1520 through the water recovery line 1538.

In addition, by pressurizing the cathode 1506 driven by the air supply pump 1539, the mixture of water and air generated in the cathode 1506 is transported to the water recovery line 1538 through the discharge port 1513, thereby passing through such a water recovery line. The mixture of 1538 and the circulation of water.

Here, with reference to the schematic diagrams shown in FIGS. 16A, 16B, 17A, and 17B, the structure of the separator 1550 included in the fuel cell filling recovery unit 1520 will be described.

As described above, the separator 1550 divides the fuel cell filling and recovering device 1520 into the filling fuel storage space 1542 containing the liquid fuel stock solution and the effluent recovery space 1541 containing water. In addition, different types of fluids are contained in the divided spaces, so it is necessary for the partition 1550 to adopt a structure that does not mix the liquids in the two chambers. Therefore, as shown in FIG. 16A and the partial enlarged view of FIG. 16A, that is, as shown in FIG. 16B, a gasket 1551 is installed on the circumference of the separator 1550 so that the circumference of the separator 1550 and the inner wall 1540b of the fuel cell filling and recovering device 1520 There is no gap between them. In addition, in order to increase the torsional rigidity of the separator 1550, the thickness of the separator 1550 is increased, for example, to a thickness of about 5 mm.

In addition, because the separator 1550 can be moved in a stable state, for example, as shown in FIG. 17B of the AA' line cross-sectional view of FIG. 17A and FIG. 17A, a guide partition can be provided inside the fuel cell filling and recovering device 1520. The guide rail 1543 of the plate 1520 is moved. As shown in FIG. 17A, such a guide rail 1543 is preferably arranged in the vertical direction, and in order to enable more stable movement, it is preferable to provide a plurality of guide rails 1543. It should be noted that, in FIG. 17A, the case where there are two guide rails 1543 is shown. In addition, in order not to generate a gap between each guide rail 1543 and the partition 1550, a gasket (not shown) is provided.

In addition, such a fuel cell system 1510 includes a control device 404 that performs integrated control while associating each operation related to the power generation of the fuel cell system 1510 with each other. The control device 404 can perform an air supply operation to 1506 based on the driving of the air supply pump 1539, and perform control of electric energy generated by the fuel cell main body 1500, and the like. In addition, an automatic control valve is used as the regulating valve 1560 or the valve 1561, and the opening and closing operations of the valves are performed by the control device 404.

Hereinafter, in the fuel cell system 1510 having such a function and structure, the supply (replenishment) operation of the fuel cell during power generation and the recovery operation of the generated water will be described. It should be noted that the control device 404 of the fuel cell system 1510 performs integrated control while associating the operations of each other to implement the following operations.

First, in the fuel cell filling and recovering device 1520, as the liquid fuel stock solution, for example, 100 ml of a methanol aqueous solution with a concentration of 63.8% by weight is contained in the filling fuel storage space 1542, and some water is contained in the effluent recovery space 1541. The state is the initial state. At this time, for example, the regulating valve 1560 and the valve 1561 are in a closed state.

Then, the regulating valve 1560 and the valve 1561 are opened, and the air supply pump 1539 is activated to supply air into the cathode 1506 through the air supply line 1537. By supplying air to the cathode 1506, the discharge recovery space 1541 is also pressurized through the water recovery line 1538. Accordingly, the separator 1550 moves toward the side of the fuel storage space 1542 for filling, the volume of the fuel storage space 1542 for filling is reduced, and the stored liquid fuel stock solution is supplied to the anode 1504 through the fuel supply line 1536. During the supply, when gas is present in the anode 1504, the gas is discharged to the outside through the exhaust valve 1511.

By supplying liquid fuel to the anode 1504, the anode reaction is performed using the liquid fuel at the anode 1504, and the cathode reaction is performed using the supplied air, which is oxygen, at the cathode 1506. According to this, a predetermined electric energy is generated by a power generating circuit not shown. In this way, by generating power by the fuel cell main body 1500, liquid fuel in an amount corresponding to the electric energy generated by the anode 1504 is consumed, and water in an amount corresponding to the electric energy is generated at the cathode 1506.

The water generated in the cathode 1506 is a mixture of the water and air, and is sent from the cathode 1506 through the discharge port 1513 to the water recovery line 1538 under the pressure of the air supply pump 1539. Then, the effluent is introduced into the gas-liquid separator 1533. During the introduction, water vapor and the like contained in the mixture are condensed in the introduction pipe 1521, and in a liquefied state, are introduced into the gas-liquid separation chamber 1533a. In addition, in the gas-liquid separation chamber 1533a, the gas 112 is stored above the gas-liquid separation chamber 1533a, and the water 110, which is the discharge, is stored below it. Accordingly, in the gas-liquid separation chamber 1533a, the mixture is separated into gas 112 and water 110.

Then, the water 110, which is the effluent stored below the gas-liquid separation chamber 1533a, is sent to the effluent recovery space 1541 through the water discharge port 1522 and the water recovery line 1538, and is recovered. The inside of the gas-liquid separation chamber 1533 is pressurized by the air supply pump 1539, so that such a water transfer operation can be performed. It should be noted that when the pressure in the gas-liquid separation chamber 1533a is above a given pressure, the gas is discharged through the pressure regulating valve 11562 to maintain the given pressure. For example, the predetermined pressure in the gas-liquid separation chamber 1533a is any pressure in the range of 2-10 kPa, preferably a pressure of about 5 kPa. In addition, instead of sending the water into the exhaust recovery space 1541 in this way, it is also possible to send water and the gas (air etc.) contained in the water.

In addition, in the fuel cell filling and recovering device 1520, by recovering water into the effluent recovery space 1541, the effluent recovery space 1541 is further pressurized, and the separator 1550 is further oriented toward the fuel storage space 1542 for filling. On the other hand, the anode 1504 consumes liquid fuel, so the pressure drops, and this pressure drop also reduces the pressure of the filling fuel storage space 1542 through the fuel supply line 1536. Therefore, the pressure of the fuel storage space 1542 for filling is lower than the pressure of the discharge recovery space 1541. Therefore, a pressure difference is generated between the two chambers. The adjacent partition 1550 moves to the side of the fuel storage space 1542 for filling. The volume of the fuel storage space 1542 is reduced. Accordingly, a part of the liquid fuel stock solution contained in the filling fuel storage space 1542 is supplied to the anode 1504 through the fuel supply line 1536, and the liquid fuel consumed at the anode 1504 is replenished.

The liquid fuel supplied to the anode 1504 in this way is used and consumed in power generation, while in the cathode 1506, water is generated along with the power generation. By repeating and continuing such an operation, while simultaneously and continuously performing the replenishment operation of the liquid fuel consumed at the anode 1504 and the recovery operation of the water generated at the cathode 1506, the fuel cell main body 1500 continues to generate a predetermined electric energy.

In addition, the air supply pump 1539 supplies air into the cathode 1506 and pressurizes the inside of the cathode 1506, so that such a liquid fuel replenishment operation and water recovery operation can be performed. In other words, the air supply pump 1539 can pressurize the discharge recovery space 1541 through the water recovery line 1538 to move the partition 1550 so that the liquid fuel stock contained in the filling fuel storage space 1541 can be removed through the fuel supply line 1536. The pressure supplied to the anode 1504 has a function of supplying air to the cathode 1506 (for example, it has such a discharge pressure).

Then, when the liquid fuel stock in the fuel storage space 1542 for filling is used up, or when power generation is stopped, the driving of the air supply pump 1539 is stopped, and the regulating valve 1560 and the valve 1561 are closed.

It should be noted that in such a fuel cell filling and recovering device 1520, the water generated by power generation is used to supply liquid fuel of approximately the same volume as the volume of liquid fuel consumed by power generation, and the water is recovered. Preferably, the volume of liquid fuel consumed by power generation and the volume of generated water are approximately the same. That is, the liquid fuel having a concentration that satisfies such a condition is, for example, an arbitrary concentration in the range of about 60 to 70% by weight. For example, it is preferable to use a methanol aqueous solution with a concentration of about 63.8% by weight.

The fuel cell system of the third embodiment described above can achieve the following various effects.

The liquid fuel supplied to the anode 1504 from the fuel cell reclaimer 1520 is diffused through the hydrophilic diffusion layer 1507 and can be supplied to the membrane electrode assembly 1502 where the catalyst is formed immediately. In particular, the end of the fuel supply line 1536 is arranged on the upper part of the anode 1504, and when the liquid fuel supplied through this end is supplied above the diffusion layer 1507, the capillary phenomenon or gravity caused by the hydrophilicity of the diffusion layer 1507 The effect is that while the liquid fuel is diffused, it is possible to uniformly and efficiently supply the entire surface of the membrane electrode assembly composed of the membrane electrode assembly 1502.

In addition, in the cathode 1506, the water generated by power generation is discharged to the diaphragm side through the diffusion layer 1508 having hydrophobicity. In addition, because the diffusion layer 1508 is hydrophobic, the water can be discharged to the outside of the cathode 1506 efficiently. In addition, the hydrophobicity of the diffusion layer 1508 and the pressurization of the air supply pump 1539 also have an effect of reducing the penetration of the liquid fuel through the membrane electrode assembly 1502 from the anode 1504 side.

In addition, in the fuel cell system 1510, the cathode 1506 generates water as effluent by generating electricity. However, the water generated in this way can be recovered in the effluent recovery space 1541 of the fuel cell filling recovery unit 1520, so this The water drains. According to this, the fuel cell system 1510 can be applied as a fuel cell system for portable electronic devices that has a feature that a fuel cell system with drainage or the like cannot be used.

In addition, by pressurizing the inside of the cathode 1506 accompanied by the air supply pump 1539 to supply air to the cathode 1506, the generated water is sent to the effluent recovery space 1541 through the water recovery line 1538 to perform such water recovery, so there is no need to install it. Dedicated power equipment for the recovery of such water (for example, a pump for effluent recovery). Therefore, the structure of the auxiliary machine system in the fuel cell system 1520 can be simplified.

In addition, even if a dedicated water recovery tank or the like is not installed for the water recovered in this way, the fuel cell filling recovery unit 1520 that reduces the amount of liquid fuel that is contained along with power generation by partitioning the water can be used as a recovery point for the water. use. Therefore, the structure of the auxiliary machine system can be simplified.

In addition, from the cathode 1504 to the water recovery line 1538, not only water is transported, but also air is mixed, that is, the mixture is transported. However, a gas-liquid separator 1533 is installed in the middle of the water recovery line 1538, so the mixture is separated into gas. And liquid, the liquid water can be recovered in the discharge recovery space 1541. Therefore, the use of a fuel cell filling recovery device with a limited storage volume enables efficient water recovery.

In addition, in the gas-liquid separator 1533, the end of the water recovery pipe 1538, that is, the introduction pipe 1521, is immersed in the water of the discharge contained in the gas-liquid separation chamber 1533a, and the contact area with the water is increased, so that the The water vapor contained in the mixture is condensed and recovered in a liquefied state. In addition, by doing this, it is possible to prevent the water from being discharged to the outside in the state of water vapor, and it is possible to provide a fuel cell system suitable for the power supply of portable electronic equipment.

In addition, along with power generation, liquid fuel is consumed in the anode 1504, but the effluent recovery space 1541 is pressurized by the recovery of water to move the separator 1550 to the side of the fuel storage space 1542 for filling to perform this consumption. Since the liquid fuel is replenished, there is no need to install a dedicated fuel supply device (fuel supply pump for filling) for replenishing the liquid fuel. Therefore, the structure of the auxiliary machine system can be further simplified.

By simplifying the structure of the auxiliary machine system in this way, the fuel cell system can be miniaturized and the electric energy self-consumed by the auxiliary machine system can be reduced. Therefore, it is possible to provide a fuel cell system suitable for a power source for portable electronic devices that is miniaturized and capable of high-efficiency power generation.

It should be noted that in the third embodiment, the fuel cell filling recovery device 1520 is not limited to the above-mentioned embodiment, and can be implemented in various other forms. FIG. 18 shows a schematic configuration of a modified example of the fuel cell filling and recovering device used in the fuel cell system according to Embodiment 3 of the present invention. It should be noted that the overall structure of the fuel cell system is substantially the same as that of the fuel cell system 1510 of the third embodiment described above, so the description thereof will be omitted.

As shown in FIG. 18, the fuel cell filling and recovering device 1620 has: a chamber partitioned by a partition 1650 that contains the liquid fuel stock solution 100, that is, a filling fuel storage space 1642; it can recover and contain water sent from the water recovery line 1638. (Or a mixture of water and gas) effluent recovery space 1641. However, the fuel cell filling and recovering device 1620 is provided with a level sensor 1652 for detecting the capacity (that is, the remaining amount) of the liquid fuel stock solution 100.

For the level sensor 1652, a magnetic sensor can be used, for example. In addition, by inserting a small detected portion 1653 made of a magnetic material into the side end portion (right side end portion in the figure) of the partition 1620, the detected portion 1653 can be detected by the level sensor 1652 in a non-contact manner. Therefore, the moving position of the partition 1650 can be detected, and the storage volume of the liquid fuel contained in the filling fuel storage space 1642 can be detected.

It should be noted that the liquid fuel storage capacity detected in this way is input into the control device 404, for example, and displayed as being identifiable from the outside of the fuel cell system.

Fig. 19 is a schematic diagram showing the external structure of the fuel cell filling and recovering device of Fig. 18.

As shown in FIG. 19, the fuel cell filling and recovering device 1620 has a fuel confirmation window 1654 which is an example of a visual recognition window that can visually recognize the remaining amount of liquid fuel stored from the outside.

As shown in FIG. 19, the separator 1650 of the fuel cell filling and recovering device 1620 is made of a color with good visibility, such as white, and a fuel confirmation window through which the separator 1650 can be visually viewed is provided on the outer shell of the fuel cell filling and recovering device 1620. 1654. In addition, by providing a scale for reading the fuel capacity at the edge of the fuel confirmation window 1654, it is possible to determine how much liquid fuel 100 is in the filling fuel storage space 1642, and whether the remaining liquid is liquid fuel 100 or discharged Water 110. Therefore, the fuel cell filling and recovering device 1620 can reliably confirm the remaining amount of liquid fuel, and for this confirmation, it does not consume electric power by itself, so it is possible to provide a fuel cell system capable of high-efficiency power generation.

It should be noted that, in this example, the partition 1650 is described as an example in which the color of the partition 1650 is white, but of course, it may also be a fluorescent color or a luminous color.

FIG. 20 is a schematic diagram showing a schematic configuration of another modified example of the fuel cell charge recovery device 35 used in the fuel cell system according to Embodiment 3 of the present invention.

As shown in FIG. 20, the fuel cell filling and recovering device 1621 has: a chamber divided by a partition 1657, that is, a filling fuel storage space 1642 that contains liquid fuel 100; it can recover and contain water or water sent in through a water recovery pipeline. The space 1641 is recovered in the exhaust of the mixture with the gas. In addition, the fuel cell filling recovery device 1621 has a position sensor 1654 for detecting the storage capacity of the liquid fuel 100.

As the position sensor 36, a magnetic sensor or an electrostatic sensor can be used, for example, and it is preferable to provide the position sensor 1654 at a plurality of positions in the moving range of the partition 1657. In addition, by inserting a small detected portion 1655 formed of a magnetic body into the side end of the partition 1657, the detected portion 1655 of the partition 1567 located at the installation position of the position sensor 1654 can be detected in a non-contact manner, and the detected portion 1655 can be detected. The moving position of the movable partition 1657.

In addition, by outputting the detection result of the position sensor 1654 to a control device or the like, it is possible to notify the remaining amount of fuel to a portable electronic device that uses the fuel cell system as a power source.

FIG. 21 is a schematic diagram showing a schematic configuration of another modified example of the fuel cell charge recovery device 35 used in the fuel cell system according to Embodiment 3 of the present invention. The overall structure of the fuel cell system is the same as that of the fuel cell system 1501 of the third embodiment described above.

As shown in FIG. 21, the fuel cell filling and recovering device 1622 is divided by a partition 1658 into a filling fuel storage space 1643 that contains liquid fuel 100, and an exhaust recovery space 1641 that can collect and contain water or a mixture of water and gas. In addition, the fuel cell filling and recovering device 1622 has: a fuel supply connector 1643 for filling the filling fuel storage space 1642 with the liquid fuel 100; and a water recovery connector for recovering the water 110 contained in the effluent recovery space 1641 1644. In addition, both the water recovery connector 1644 and the fuel supply connector 1643 have leak prevention mechanisms. It should be noted that when water and gas are contained in the effluent recovery space 1641, the gas can be recovered together with the water through the connector 1644 for water recovery.

FIG. 22 is a schematic diagram showing the connection state of the fuel cell filling recovery unit 1622 and the regenerator 3600 during regeneration. The regenerator 3600 shown in FIG. 22 is the same as the regenerator 3300 shown in FIG. The piston 3620 moved by the 3610a; the plug parts 3635 and 3636 that are respectively engaged with the fuel replenishing connector 1643 and the water recovery connector 1644 provided in the fuel cell filling and recovering device 16222.

The piston 3620 has: a partition 3621 that divides the regenerator housing 3610 into an exhaust accommodating portion 3611 and a filling fuel supply portion 3612; is protrudingly provided on the partition 3621, extends along the axial direction 3610a, and penetrates the regenerator housing 3610, reach the outside pole 3622.

Next, the regeneration operation of the fuel cell filling recovery unit 1622 using the regenerator 3600 having the above structure will be described. It should be noted that the regenerator 3600 is in a state of being filled with the filling fuel 102, and the fuel cell filling and recovering device 1622 is in a state of being filled with the exhaust 110 to some extent or completely.

As shown in FIG. 22, the water recovery connector 1644 of the discharge recovery space 1641 of the fuel cell filling recovery unit 1622 and the plug part 3636 of the discharge storage portion 3611 of the regenerator 3600 are connected, and the fuel cell filling recovery unit The refueling connector 1643 of the fuel storage space 1642 for filling of 1622 and the plug part 3635 of the filling fuel supply part 3612 of the regenerator 3600 are connected. According to this, the exhaust material recovery space 1641 and the exhaust material storage portion 3611 communicate with each other, and the filling fuel storage space 1642 and the filling fuel supply portion 3612 communicate with each other. It should be pointed out that Figure 8 shows before the regeneration operation.

Next, the operator presses the rod 3622 of the piston 3620 in the axial direction 3610a. By pressing the piston 3620 toward the filling fuel supply part 3612, the filling fuel 102 contained in the filling fuel supply part 3612 of the regenerator 3600 is supplied to the fuel cell filling recovery unit 1622 through the plug part 3635 and the fuel supply connector 1643. The filling fuel storage space 1642. By supplying the filling fuel 102 to the filling fuel storage space 1642, the separator 1658 of the fuel cell filling recovery device 1622 presses the exhaust material 110 in the exhaust material recovery space 1641. Accordingly, the effluent 110 is supplied to the effluent accommodating portion 3611 of the regenerator 3600 through the water recovery connector 1644 and the plug portion 3636. In this way, the filling fuel 102 fills the fuel cell filling recoverer 1622, and the effluent 110 fills the regenerator 3600. That is, in the regeneration of the fuel cell filling and recovering device 1622, the filling and recovery of the liquid fuel can be performed at the same time.

It should be noted that the water recovery connector 1644 and the plug portion 3636, the plug portion 363 and the fuel replenishing connector 1643 are respectively realized by connectors composed of the socket portion and the plug portion shown in FIGS. 10A and 10B.

It should be pointed out that the installation positions of the fuel supply connector 1643 and the water recovery connector 1644 of the fuel cell filling and recovering device 1622 are as shown in the schematic diagrams of the fuel cell filling and recovering device 1642 of FIG. 23A and FIG. 23B. A fuel supply connector 1643 is provided above the upper limit position of the movement range of the partition 1658 (refer to FIG. 23A), and the connector for water recovery is arranged below the lower limit position of the movement range (refer to FIG. 23B). 1644. With this arrangement, the capacity of the fuel cell filling and recovering device 1622 can be utilized to the maximum, and liquid fuel can be supplied and water can be recovered.

FIG. 24 is a schematic diagram showing a schematic configuration of a fuel cell system 1710 according to Embodiment 4 of the present invention. As shown in FIG. 24, the fuel cell system 1710 has a fuel cell main body 1700 having a different structure from that of the fuel cell system 1510 of the third embodiment, but has the same structure as the fuel cell system 1510 with respect to the structure of other auxiliary machinery systems. Only the different configurations are explained below. It should be noted that, as shown in FIG. 24, the fuel cell system 1710 is provided with a fuel cell main body 1700, an air supply pump 1739, a gas-liquid separator 1733, a valve 1761, a fuel cell filling recovery device 1720, and an exhaust recovery space 1741. , Filling fuel storage space 1742 and adjusting valve 1760.

As shown in FIG. 24, the fuel cell system 1710 has the anode 1704 of the fuel cell main body 1700 arranged in its inner space, and has a fuel mixing tank 1732 that can accommodate the anode 1740 and the liquid fuel supplied from the fuel cell filling recovery device 1720.

In addition, the anode 1704 of the fuel cell main body 1700 has a fuel supply port 1709 arranged in the lower part of the figure, and a discharge port 1714 of gas such as carbon dioxide arranged in the upper part of the figure. In addition, the anode 1704 is arranged such that the fuel supply port 1709 is immersed in the liquid fuel contained in the fuel mixing tank 1732. Accordingly, the liquid fuel can be supplied into the anode 1704 through the fuel supply port 1704. In addition, the fuel mixing tank 1732 is provided with an exhaust valve 1711 that exhausts gases such as carbon dioxide.

Here, FIG. 25 is a schematic diagram showing a more detailed structure of the fuel cell main body 1700. As shown in FIG. 25, the fuel cell main body 1700 has an anode-side diffusion layer 1704d and a cathode-side diffusion layer 1706d, a membrane electrode assembly 1702 arranged in between, an anode-side catalyst layer 1702a, and a cathode-side catalyst layer 1702b, The anode side diaphragm 1704s, the cathode side diaphragm 1706s, and the casings 1704h and 1706h. The electrolyte membrane 1702, the anode-side catalyst layer 1702a, and the cathode-side catalyst layer 1702b are referred to as a membrane electrode assembly. As the electrolyte membrane 1702, for example, an electrolyte membrane whose permeation of liquid fuel is 1/10 of the conventional one is used. The membrane-electrode assembly is formed on one surface of the electrolyte membrane 1702 as an anode catalyst 1702a, which is formed by dispersing platinum and ruthenium, or an alloy of platinum and ruthenium on a carbon-based powder carrier, and on the other surface as an anode catalyst 1702a. The cathode catalyst 1702b is formed of a material in which platinum particles are dispersed and supported on a carbon-based carrier. The diffusion layer 1704d on the anode side is formed by, for example, hydrophilizing carbon paper, and the diffusion layer 1706d on the cathode side is formed by performing hydrophobic treatment on carbon paper, for example. It should be pointed out that such a hydrophilic treatment can improve the hydrophilicity by activating the carbon paper with water vapor. In addition, the hydrophobic treatment imparts hydrophobicity by impregnating carbon paper with a dispersion of a fluorine resin such as polytetrafluoroethylene. After each diffusion layer is closely attached to the membrane electrode assembly, the anode side diaphragm 1704s and the cathode side diaphragm 1706s are fixed by the casings 1704h and 1706h, and the fuel cell main body 1700 can be formed. In addition, the diffusion layers 1704d and 1706d can also be used as electrodes.

FIG. 26A shows a front view of the cathode side separator 1706s, and FIG. 26B shows a cross-sectional view taken along the line BB' of the cathode side separator 1706s in FIG. 26A. As shown in FIGS. 26A and 26B, the cathode side diaphragm 1706s is formed of, for example, a non-conductive resin, and is composed of a plate-shaped main body 501 flat in the thickness direction, and a groove 502, which is an example of unevenness, is provided on one surface. The cathode side diaphragm 302s is in contact with the membrane electrode assembly, and the surface on the side where the groove 502 is provided is pressed against the cathode side diffusion layer 1706d, and the area surrounded by the groove 502 and the cathode side diffusion layer 1706d is formed as a passage for air . The groove 502 provided on the surface of the cathode side diaphragm 1706s is provided in a serpentine shape between the upper end and the lower end of the plate-shaped main body 501. In addition, since the inlet 503 connected to the air supply port of the cathode 1706 is connected to the discharge port 504 connected to the discharge port of the cathode 1706, the air supplied from the air supply port of the cathode 1706 passes through the inlet 503 through the discharge port 504. , Is discharged to the outside from the discharge port of the cathode 1706.

FIG. 27 is a schematic diagram showing the structure of the anode-side separator 1704s used in the anode 1704.

As shown in Fig. 27, the anode side diaphragm 1704s is arranged so that the main body 510 has a wave plate shape (an example of unevenness) that is flat in the thickness direction. The top line 515 of the wave is along the direction connecting the fuel supply port and the discharge port of the anode 1704 . In this embodiment, the distance between the top lines 515 of adjacent waves is approximately 1 to 5 mm, and the thickness of the diaphragm 1704s, that is, the amplitude of the wave is approximately 1 to 5 mm. For example, the diaphragm 1704s can be provided with four or more grooves on the anode 1704 side.

In addition, the anode-side diaphragm 1704s forms passages 511 and 512 through which the liquid fuel passes in the trough portions surrounded by the inner wall of the casing 1704h and the surface of the diffusion layer 1704d (membrane electrode assembly) that are in contact with the top line 515 of the adjacent wave. . The anode-side diaphragm 1704s shown in FIG. 27 is viewed from above and has a sine wave shape in cross section. Therefore, the area of the passage 512 on the case side and the passage 513 on the membrane electrode assembly side are approximately the same.

In addition, in the fuel cell main body 1700, the discharge port is set higher than the fuel supply port, so the liquid fuel flows into the passages 511 and 512 of the anode 1704, and the carbon dioxide generated by the anode reaction using the liquid fuel rises to The direction of the discharge port of the anode 1704 is discharged. Along with this rise in carbon dioxide, the liquid fuel in the anode 1704 also moves in the above-mentioned direction, and is discharged from the discharge port of the anode 1704 to the outside. If the liquid fuel in the anode 1704 rises, the liquid fuel stored in the fuel mixing tank 1732 flows into the anode 1704 from the fuel supply port of the anode 1704. In addition, the carbon dioxide generated in the anode 1704 can be efficiently discharged.

It should be pointed out that instead of using carbon paper for the diffusion layer, carbon cloth can be used. As the electrolyte membrane 1702, for example, three sheets of Nafion (trade name) of DuPont Co., Ltd. can be stacked to reduce permeation. In addition, as the electrolyte membrane 1702, for example, a porous membrane having submicron-order pores may be filled with a pore-filled electrolyte membrane filled with an electrolyte polymer, or a ceramic porous body may be filled with an electrolyte polymer.

In the fuel cell system 1710 having such a structure, the fuel supplied from the fuel cell filling recovery unit 1720 to the fuel mixing tank 1732 is supplied to the anode 1704 through the fuel supply port 1709. In the anode 1704, the liquid fuel is sucked up and diffused by the capillary phenomenon of the hydrophilic diffusion layer 1704d, and is supplied to the surface of the membrane electrode assembly 1702 to undergo an anode reaction. In the cathode 1706, the water generated on the surface of the membrane electrode assembly 1702 by the cathode reaction is discharged from the diffusion layer 1706d. Since the diffusion layer 17006d is hydrophobic, the water is discharged to the outside of the cathode 1706 with good drainage. In addition, the hydrophobicity of the diffusion layer 1706d and the pressurization of the air supply pump 1739 can reduce the penetration of the liquid fuel through the membrane electrode assembly 1702 from the anode 1704 side.

It should be noted that, in the fourth embodiment, an example of using carbon paper as the diffusion layer is described, but carbon cloth or foamed metal materials can be used.

FIG. 28 is a schematic configuration diagram of a fuel cell system according to Embodiment 5 of the present invention. As shown in FIG. 28, the fuel cell system 1810 has: a fuel cell main body 1800 that converts the chemical energy of the fuel into electric energy by electrochemical conversion to generate electricity; and a fuel cell main body 1800 that supplies fuel necessary for power generation to the fuel cell main body 1800. Auxiliary system. The fuel cell main body 1800 is a fuel cell system using a direct methanol fuel cell (DMFC) that uses a methanol aqueous solution, an example of organic liquid fuel, as a fuel, and directly extracts protons from methanol to generate electricity.

As shown in FIG. 28, the fuel cell main body 1800 has an anode (fuel electrode) 1804, a cathode (air electrode) 1806, and a membrane electrode assembly 1802. The anode 1804 performs an oxidation reaction on the supplied methanol, and performs a reaction for extracting protons and electrons (anode reaction). The electrons move to the cathode 1806 through an external circuit (not shown) that electrically connects the anode 1804 and the cathode 1806, and the protons move to the cathode 1806 through the membrane electrode assembly 1802. In addition, the cathode 1806 performs a reaction (cathode reaction) that reduces oxygen supplied from the outside and protons moved from the anode 1804 through the membrane electrode assembly 1802 with electrons flowing through the external circuit to produce water (cathode reaction). In this way, the oxidation reaction proceeds at the anode 1804, and the reduction reaction proceeds at the cathode 1806, and electrons flow to the electrode wires (not shown) to generate power.

Specifically, the membrane electrode assembly 1802 is used as an electrolyte membrane, using DuPont's Nafion (trade name), on one surface of the electrolyte membrane, as an anode catalyst for the anode 1804, formed on a carbon-based powder carrier to disperse and support platinum And ruthenium, or platinum and ruthenium alloy material. By placing an electrode and diffusion layer (not shown) made of carbon paper on both ends of the membrane electrode assembly 1802 in close contact with the anode catalyst and the cathode catalyst, the anode side diaphragm and the cathode are interposed therebetween. The side diaphragm is fixed on the shell and assembled.

In addition, as shown in FIG. 28, the anode 1804 has: a fuel supply port 1809 and a water supply port 1830 for supplying methanol and water necessary for carrying out the anode reaction to the inside of the anode; Carbon dioxide or the remaining methanol aqueous solution not used in the reaction is discharged from the discharge port 1831 from the inside.

In addition, the cathode 1806 has: in order to supply oxygen used in the implementation of the cathode reaction, for example, air is used, and the air is supplied to an internal air supply port 1812; and water (an example of the product generated in the cathode reaction) is discharged ( Including any state of liquid or gaseous state, or a state in which each state is mixed), and a discharge port 1813 for unused air in the reaction. It should be noted that this product contains water as a main component, but sometimes also contains formic acid, methyl formate, methanol (due to permeation described later) and the like.

Next, the structure of the auxiliary machine system of the fuel cell system 1810 will be described. The structure of the auxiliary equipment system includes: an auxiliary equipment structure for supplying methanol aqueous solution to the anode 1804 of the fuel cell main body 1800; an auxiliary equipment structure for supplying air to the cathode 1806; and an auxiliary equipment structure for recovering exhaust generated by the cathode 1806. The auxiliary machinery structure of the thing that is water.

As shown in FIG. 28, as an auxiliary structure for the fuel supply, there are: a fuel container 10 that accommodates and can supply a methanol aqueous solution as a liquid fuel stock solution to the anode 1804; and connects the fuel cell replenisher 1820 and the anode The fuel supply pipe 1871 of 1804; the fuel regulating valve 1860 provided in the middle of the fuel supply pipe 1871. In addition, a concentration detector 1832 that detects the fuel concentration in the anode is provided in the anode 1804 of the fuel cell main body.

First, a description will be given of the filling recovery device for a fuel cell. Fig. 29 is a schematic diagram showing the structure of a fuel cell reclaimer used in the fuel cell system of Fig. 28. As shown in FIG. 29, the fuel cell filling and recovering device 1820 has: a container body 1840, a filling fuel storage space 1842, an effluent recovery space 1841, a partition 1850, an effluent inlet 1843, a heat radiating pipe 1821, a water supply port 1844 , Fuel supply port 1845, gas discharge port 1846, pressure regulating valve 1862.

In the fuel cell filling and recovering device 1820, the interior of the container body 1840 is partitioned by the partition plate 1850, and an exhaust recovery space 1841 is formed on the upper side, and a filling fuel storage space 1842 is formed on the lower side. The partition 1850 is provided to be able to move in parallel in the vertical direction in FIG. 29. By changing the position of the partition 1850, the volume of the effluent recovery space 1841 and the filling fuel storage space 1842 is changed.

A raw liquid of liquid fuel is stored in the fuel storage space 1842 for filling. As the raw liquid of the liquid fuel, methanol, dimethyl ether, and their aqueous solutions, etc. can be used, but in this embodiment, 63.8% by weight of methanol is used.

The effluent recovery space 1841 stores water in the initial stage of use. Preferably, the occupancy rate of the exhaust material recovery space 1841 in the fuel cell filling recovery device 1820 is small, and specifically, it is preferably 20% or less. If the occupancy rate exceeds 20%, the initial fuel occupancy rate in the fuel cell filling recovery device 1820 decreases, and therefore the storage amount of fuel decreases.

The partition 1850 is used to divide the filling fuel storage space 1842 and the exhaust recovery space 1841, and a material with low permeability for water or liquid fuel is used. As the material, for example, polymer resins such as polyethylene terephthalate, polycarbonate, and Teflon (trade name), and metals such as glass, aluminum, and stainless steel can be used. When the thickness of the separator is thin, the initial fuel occupancy rate of the fuel cell filling and recovering device is increased, so it is good, but if it is too thin, the pressure of the fuel ejected from the filling fuel storage space 1842 will be strong when pressurized. May be insufficient. Therefore, according to the design of the fuel cell system using the fuel cell filling and recovering device, the structure of the separator, such as the material used, the shape, and the like, is different.

As shown in FIG. 30, the partition 1850 is provided with a rubber gasket 1851 around the partition body 1850 a in order to improve the sealing performance between the partition 1850 and the container body 1840. In addition, as shown in Figs. 28 and 29, a magnet 1855 is provided on a part of the periphery. As described later, this magnet 1855 is used for position detection of the partition 1850 and used for processing for calculating the remaining amount of liquid fuel stored in the fuel storage space 1842 for filling.

When the thickness of the partition 1850 is thin, the partition 1850 may be difficult to move in parallel as a whole. Therefore, the thickness T of the partition 1850 is preferably thick to a certain extent.

In addition, as shown in FIG. 31, the partition 1850 moves in parallel within the container body 1840 by a distance D from the upper limit position to the lower limit position. When the partition 1850 is at the upper limit position, the fuel storage space 1842 for filling is in a state where the most fuel is stored. This position is near the lower side of the water supply port 1844 and is lower than the lower side of the heat radiating pipe 1821. In addition, when the partition 1850 is located at the lower end position indicated by 1850x in FIG. 31, it is in a state of being filled with fuel. This position may be the lowermost end of the container, but it is preferable to have a slight margin.

The container body 1840 has a strength that does not break under the pressure applied to the discharge recovery space 1841. If it is a material that does not leak water or liquid fuel, it is not particularly limited, but for example, polyethylene terephthalate can be used. Or polymer resins such as polycarbonate and Teflon (trade name), and metals such as glass, aluminum, and stainless steel. However, in order for the magnetic field from the magnet 1855 attached to the partition 1850 to reach the outside of the container, it is necessary to be a non-magnetic body. Under these conditions, polymer resins are particularly suitable from the viewpoint of lightness and strength.

The exhaust inlet 1843 is detachably connected to the cathode 1806 of the fuel cell main body 1800 through the connectors 1860 and 1861, and is detachably connected through the exhaust supply pipe 1874 to supply the exhaust containing water and air discharged from the cathode 1806 to the exhaust. Reclaim space 1841. The temperature of the effluent from the cathode 1806 is approximately 60-80°C and contains water, water vapor, air, and the like. A heat release pipe 1821 is connected to the discharge inlet 1843, and the discharge from the cathode is condensed when passing through the heat release pipe 1821, and water and air are separated. It should be pointed out that when water is stored in the discharge recovery space 1841, the water acts as a cooling medium for the heat release pipe 1821 to separate water and air in a shorter time.

The pressure regulating valve 1862 is connected to the gas discharge port 1846 of the container main body 1840, and when the pressure in the discharge recovery space 1841 reaches a certain level or higher, it automatically adjusts to reduce the pressure. The pressure regulating valve 1862 can use polymer resins such as polyethylene or polypropylene, and metals such as aluminum or stainless steel. A gas-liquid separation membrane (not shown) is arranged at the gas discharge port 1846 to prevent water and the like from leaking from the pressure regulating valve. As the material of the gas-liquid separation membrane, for example, a fluorine-based FEP resin or the like is exemplified, and the thickness thereof is usually 10 to 1000 microns.

The water supply port 1844 is detachably connected to a pipe 1872 connected to the anode 1804 side of the fuel cell main body 1800 through connectors 1862 and 1863, and supplies water stored in the effluent recovery space 1841 to the anode 1804 side. In order to control the amount of water supplied to the fuel cell main body 1800 through the water supply port 1844, as described later, a water valve 1833 is provided on the pipe 1872 connecting the exhaust recovery space 1841 and the anode 1804.

The fuel supply port 1845 is arranged near the bottom of the fuel cell reclaimer 1820, and is detachably connected to one end of the fuel supply pipe 1871 through connectors 1864 and 1865. According to this, the liquid fuel stock solution contained in the filling fuel storage space 1842 can be transported through the fuel supply pipe 1871. The thrust for the supply of the liquid fuel stock solution at this time is the leaning force of the separator 1850 in the direction of the filling fuel storage space 1842 due to the increase in the pressure in the effluent recovery space 1841 as described later.

As the auxiliary structure of the air supply, there is an air supply pipe 1857 connected to the air supply port 1812 of the cathode 1806; it is arranged in the middle of the air supply pipe 1857 and supplies air into the cathode 1806 through the air supply pipe 1857. The air supply pump 1839. As the air supply pump 1839, it is preferable to use a small size and low power consumption, for example, a motor pump (with a check valve, discharge volume: 0 to 2L/min, discharge pressure: 30kPa). When used, for example, 1L/min supply air. In addition, when power generation is performed by the fuel cell main body 1800, the air supply pump 1839 is driven to supply necessary oxygen into the cathode 1806, and when the power generation is stopped, the driving of the air supply pump 1839 is stopped. It should be noted that when power generation is stopped, the fuel supply is also stopped by closing the fuel regulating valve 1860.

As an auxiliary structure for water recovery, it is provided with the discharge port 1813 connecting the cathode 1806 and the discharge inlet 1843 of the fuel cell filling recovery device 1820, and the discharge containing water and air generated by the cathode 1806 is supplied, The effluent supply pipe 1838 recovered to the fuel cell filling and recovering device 1820; connects the water supply port 1843 of the effluent recovery space 1841 of the fuel cell filling and recovering device 1820 and the cathode 1806 of the fuel cell main body 1800 to store in the fuel The water in the discharge recovery space 1841 of the battery filling recovery device 1820 is supplied to the water supply pipe 1872 of the fuel cell main body 1800; and a water valve 1833 that adjusts the amount of water passing through the water supply pipe 1872.

The thrust of the discharge flow of the discharge supply pipe 1838 is the driving of the air supply pump 1839 to pressurize the inside of the cathode 1806, and the discharge generated in the cathode 1806 is transported into the discharge supply pipe 1838 through the discharge port 1813. The thrust of the water flow of the water supply pipe 1872 is the pressure in the discharge recovery space 1841 of the fuel cell filling recovery device 1820 as described later.

The fuel cell system 1810 in FIG. 28 includes a control device 405 that controls the operation of each device or component equipment. Based on the output from the concentration detector 1832 provided in the anode 1804 of the fuel cell main body 1800, the control device 405 controls the air supply operation of the air supply pump 1839, the water valve 1833, and the fuel adjustment valve 1860 for the fuel cell system 1810. The control of each operation such as the opening adjustment operation is related to each other, and the overall control is performed to establish the material balance described later.

In addition, the control device 405 drives the air supply valve 1839 when the fuel cell main body 1800 is generating power, supplies air to the cathode 1806 side, opens the fuel regulating valve 1860 and opens the water valve 1833 as necessary to supply liquid to the anode 1804 side. Fuel and water. When this power generation is stopped, the operation of the air supply pump 1839 is stopped and the water valve 1833 and the fuel regulating valve 1860 are closed.

A hall element 1834 is installed near the fuel cell recharger 1820 to non-contact detect the magnetic field emitted from the magnet 1855 provided on the fuel cell separator 1850, detect the position of the magnet 1855, and send it to the control device 405 information. The control device 405 calculates the remaining amount of fuel in the fuel cell filling recovery device 1820 based on the position of the separator 1850.

Next, the operation of each component device when generating power in the fuel cell system 1810 of FIG. 28 will be described.

First, in the fuel cell system 1820 of FIG. 28, the air supply pump 1839 is driven according to an instruction from the control device 405, and oxygen, which is air, is supplied to the cathode 1806 through the air supply pipe 1857 and the air supply port 1812. The air passing through the cathode is supplied to the fuel cell filling recovery device, and the fuel cell filling recovery device is pressurized. At start-up, no reaction occurs at the cathode, so only air is introduced into the filling recovery device for the fuel cell. At this time, the pressure is adjusted to be higher than during operation by the pressure adjusting valve 1862, and the anode 1804 of the fuel cell main body 1800 is supplied with, for example, a 63.8% methanol aqueous solution (liquid fuel).

Then, by supplying fuel to the anode, the anode reaction proceeds at the anode 1804 and the cathode reaction proceeds at the cathode 1806. The carbon dioxide generated by the anode reaction at the anode 1804 is discharged to the outside of the fuel cell main body 1800 through the discharge port 1831. The hydrogen ions generated by the anode reaction penetrate to the cathode, and if the cathode reaction starts, electricity is generated between the anode 1804 and the cathode 1806, that is, in the power generation circuit.

The discharge containing water and air generated at the cathode 1806 due to the cathode reaction contains water and air. The inside of the cathode 1806 is pressurized by the air supply pump 1839, and is delivered to the discharge supply pipe 1838 through the discharge port 1813. The conveyed effluent is supplied to the fuel cell filling recovery unit 1820 through the effluent supply pipe 1838.

In addition, by performing the power generation, the methanol and water in the anode 1804 are consumed. Accordingly, methanol corresponding to the reduced portion of the methanol aqueous solution in the anode 1804 is supplied from the filling fuel storage space 1842 of the fuel cell filling recovery device 1820. In addition, as necessary, water is supplied from the discharge recovery space 1841 of the fuel cell filling recovery device. The opening positions of the fuel control valve 1860 and the water valve 1833 are controlled by the control device 405 to determine the amount of methanol and water to be supplied.

By continuously and repeatedly performing this operation, the fuel cell main body 1800 continues to generate necessary electric energy (predetermined electric energy). When power generation is stopped in the fuel cell system 1810, the air supply pump 1839 is stopped, and the fuel control valve 1860 and the water valve 1833 are closed.

Next, a specific example of the material balance of the fuel cell system 1810 of FIG. 28 will be described. This example is the material balance under ideal conditions. In fact, there are error factors such as permeation in the fuel cell main body 180, outflow of water generated from the cathode 1806 side, and unreacted fuel supplied to the anode 1804 side. . In this example, the 63.8 wt% methanol aqueous solution stored in the filling fuel storage space 1842 of the fuel cell filling collector 1820 is mixed at the same ratio as the ratio of methanol and water consumed during power generation. There will be no excessive shortage, and the reaction will proceed.

It should be noted that the membrane electrode assembly 1802 of the fuel cell main body 1800 is formed so as not to pass water or methanol, but so-called permeation occurs in which water or methanol passes. The higher the concentration of the methanol aqueous solution, the tendency for the permeation to increase.

In order to reduce permeation, it can be achieved by overlapping multiple (for example, three) membranes constituting the membrane electrode assembly 1802. In the following description of the material balance, in order to facilitate the understanding of the description, it is assumed that no permeation occurs in the membrane electrode assembly.

At the beginning of power generation, the anode 1804 is first supplied with 11.7 ml of fuel using the pressure of the air supply pump 1839 on the cathode side. At this time, the amount of fuel stock was reduced to 88.3ml. In the anode 1804, 6.4 g (8.1 ml) of methanol and 3.6 g (3.6 ml) of water in the liquid fuel are consumed, and in the cathode 1806, 10.8 g (10.8 ml) of water is produced. When fuel is supplied to the anode 1804, the anode 1804 and the cathode 1806 respectively react to start power generation.

Next, 10.8 mg (10.8 ml) of water produced at the cathode 1806 is introduced into the exhaust material recovery space 1841 of the fuel cell filling recovery device 1820. At this time, due to the increase in water, the volume of the effluent recovery space 1841 is increased. The partition 1850 is pressurized and moved to the side of the fuel storage space 1842 for filling, and liquid fuel is supplied to the 10.8mg (10.8ml) portion of the increased water. anode.

In order to supply the same amount as the first supply amount, the opening of the valve is adjusted based on the control device 405, and the pressure adjustment valve 1862 is used to pressurize at a higher pressure than normal, so that the partition 1850 is moved, and the supply is insufficient. 0.9ml of fuel. At this time, by the supply of the liquid fuel, the amount of the liquid fuel stock solution stored in the filling fuel storage space 1842 of the fuel cell filling and recovering device 1820 after the power generation is reduced to 76.6 ml. In addition, 10.8 ml of water generated by the cathode 1806 is stored in the effluent recovery space 1841. Therefore, in the fuel cell filling and recovering device 1820, a total of 87.4 ml of liquid of 76.6 ml of liquid fuel and 10.8 ml of water is stored at this time.

By repeating power generation, supply of liquid fuel, and recovery of produced water in this way, the amount of the liquid fuel stock solution 100 contained in the filling fuel storage space 1842 of the fuel cell filling and recovering device 1820 is reduced, and is stored in the effluent recovery space 1841 The amount of water 110 in the battery increases. The separator 1850 of the fuel cell filling and recovering device 1820 moves to the side of the filling fuel storage space 1842 with the decrease in the amount of the liquid fuel stock solution 100 and the increase in the amount of the water 110 stored in the effluent recovery space 1814. The fuel storage space 1842 for filling is pressurized. In addition, actually, the air discharged from the cathode 1806 flows into the effluent recovery space 1841 of the fuel cell filling and recovering device 1820 together with water. Therefore, due to the air pressure, the pressure of the effluent recovery space 1841 of the fuel cell filling and recovering device 1820 is The increase acts as a leaning force for pressing the partition 1850. It should be pointed out that when the pressure in the discharge recovery space 1841 is too high, the pressure is automatically adjusted to a given value by opening the pressure adjustment valve 1862 provided on the outer wall of the discharge recovery space 1841.

As the liquid fuel stock solution 100 is consumed, the partition 1850 moves to the side of the fuel storage space 1842 for filling. As described above, the separator 1850 is provided with a magnet 1855, and the magnetic field generated from the magnet passes through the fuel cell container main body 1840 and is detected by the Hall element 1834 provided near the fuel cell refill 1820. The Hall element 1834 is provided in a non-contact with the magnet 1855, detects the position of the magnetic field from the magnet 1855, measures the position of the partition 1850, and sends the information to the control device 405.

Next, the control device 405 will be described. FIG. 22 is a block diagram showing the structure of the control device 405. As described above, the control device 405 performs various operation controls of the fuel cell. Specifically, the operation management of the fuel cell system, the adjustment control of the fuel concentration supplied to the anode side of the fuel cell main body 1800, and the detection of the amount of fuel remaining in the fuel cell reclaimer. The control device 405 has functional blocks such as an operation management unit 405a, a concentration comparison unit 405b, a valve opening degree calculation unit 405c, a fuel remaining amount calculation unit 405d, a residual electric energy calculation unit 405e, a power consumption calculation unit 405f, and a residual time calculation unit 405g.

The operation management unit 405a is responsible for the operation management of the entire fuel cell system, such as starting and stopping of auxiliary machinery. The operation management unit stores various information necessary for operation management for establishing the above-mentioned material balance.

The concentration comparison unit 405 b and the valve opening degree calculation unit 405 c perform adjustment control of the fuel concentration supplied to the anode side of the fuel cell main body 2. The concentration comparison unit 405c compares the information of the fuel concentration in the anode output from the concentration detector 1832 with a preset value stored in advance, and detects whether the fuel concentration in the anode is within an appropriate range. When the result is that the fuel concentration in the anode is not within the appropriate range, in order to bring it back to the appropriate range, the valve opening calculation unit 405c calculates the water valve 1833 and the fuel regulating valve 1860 that determine the amount of fuel and water supplied to the anode. The operation management unit operates the water valve 1833 and the fuel adjustment valve 1860 to adjust the supply amount.

The fuel remaining amount calculating unit 405d, the remaining electric energy calculating unit 405e, the consumed electric energy calculating unit 405f, and the remaining time calculating unit 405g detect the amount of fuel remaining in the fuel cell filling and recovering device. Based on the information about the position of the separator detected by the Hall element 1834, the fuel remaining amount calculation unit 405d calculates the amount of remaining fuel contained in the fuel cell filling and recovering device. The remaining power calculation unit 405e calculates the amount of electricity generated by the liquid fuel contained in the fuel cell filling recovery device based on the fuel remaining volume calculated by the fuel remaining volume calculation unit 405d and the concentration of the fuel contained in the fuel cell filling recovery device. The residual amount of electricity.

In addition, the power consumption calculation unit 405f calculates the predicted amount of power generation for one hour from the current power generation of the fuel cell system. The remaining time calculation unit 405g calculates the energy to be stored in the fuel cell filling recovery device based on the remaining power that can be generated by the remaining power calculation unit 405e and the predicted amount of one hour of generated power calculated by the power consumption calculation unit 405f The remaining predicted time for liquid fuel power generation. The remaining fuel amount stored in the fuel cell reclaimer and the remaining estimated time that can be generated are output to the electronic equipment equipped with the fuel cell system outside the control device, and can be used in the display of the remaining fuel amount of the electronic equipment.

It should be noted that, as a modification of the calculation method of the predicted amount of one-hour power generation calculated by the power consumption calculation unit 405f, the time elapsed change in the power generation amount of the fuel cell can be stored, and based on the time elapsed change in the power generation amount, 1 The predicted amount of electricity generated per hour.

It should be pointed out that in the description of the material balance, for ease of understanding, in the initial state, after all the liquid fuel provided to the anode 1804, that is, methanol is consumed, the methanol is supplied from the fuel cell filling recovery unit 1820, but in actual During the operation, the supply of methanol is continuously performed. In this embodiment, power generation can be continuously performed until the liquid fuel stock solution 100 stored in the fuel cell filling and recovering device 1820 is used up. Even if the water generated in the power generation is completely recovered, the total volume of the fuel cell filling and recovering device 1820 is It does not increase, and even if a tank for recovering water is not separately prepared, the fuel can be filled to the allowable volume of the fuel cell filling and recovering device 1820.

In addition, since the water and air stored in the effluent recovery space 1841 of the fuel cell filling and recovering device 1820 move the separator 1850 to the side of the filling fuel storage space 1842, it is used to remove the fuel cell filling and recovering device 1820. The power source for supplying the liquid fuel 100 does not require a pump or the like, and the self-consumption power of the fuel cell system 1810 can be reduced. In addition, the remaining amount of fuel in the fuel cell filling and recovering device 1820 can be calculated based on the position of the separator 1850, so this information can be used in the display of the switching time of the fuel cell filling and recovering device 1820, etc.

It should be noted that in the fifth embodiment, in order to reduce permeation, an example of overlapping multiple electrolyte membranes is shown. However, it is possible to fill the electrolyte with pores filled with electrolyte polymer in a porous membrane with submicron pores. Membrane or material filled with electrolyte polymer in a ceramic porous body.

Next, a fuel cell system according to Embodiment 6 of the present invention will be described. FIG. 33 is a schematic configuration diagram of a fuel cell system according to Embodiment 6 of the present invention. The fuel cell system 1910 of this embodiment has substantially the same structure as the fuel cell system 1810 of the fifth embodiment, and the description will be focused on the differences.

The fuel cell system 1910 of this embodiment is a fuel cell system using a direct methanol fuel cell (DMFC) that generates power by directly extracting protons from methanol. The structure of the fuel cell main body 1900 is almost the same as the fuel cell system 1810 of the first embodiment. Yes, but as shown in FIG. 33, a part of the structure is different, that is, the fuel cell main body 1900 is installed such that the anode 1904 side is immersed in the fuel mixing tank 1932, which is an auxiliary machine for fuel supply.

Fig. 34 is a diagram showing a schematic configuration of a fuel cell main body used in the fuel cell system of Fig. 33. As shown in Figs. 33 and 34, the fuel cell system 1910 has: a fuel cell main body 1900 that converts the chemical energy of the fuel into electrical energy by electrochemical conversion to generate electricity; and supplies the fuel necessary for power generation to the fuel cell. Auxiliary system of the main body 1900. In addition, the fuel cell system 1910 is a direct methanol fuel cell (DMFC) that uses methanol aqueous solution as an example of organic liquid fuel as fuel, and directly extracts protons from the methanol to generate electricity.

As shown in FIGS. 33 and 34, the fuel cell main body 1900 has an anode (fuel electrode) 1904, a cathode (air electrode) 1906, and a membrane electrode assembly 1902. In the membrane electrode assembly 1902, catalyst layers 1902a and 1902c are respectively joined to both sides of the electrolyte membrane 1902b. The anode 1904 oxidizes the supplied methanol to perform a reaction (anode reaction) for extracting protons and electrons.

The anode 1904 has a fuel supply port 1919 for supplying the methanol aqueous solution necessary for the anode reaction to the inside, and is used to discharge carbon dioxide generated by the anode reaction or the remaining methanol aqueous solution not used in the reaction from the inside. The discharge port 1914. The discharge port 1914 is provided at a position higher than the fuel supply port 1919.

The cathode 1906 has: in order to supply oxygen necessary for the cathode reaction, for example, air is used, and an air supply port 1912 for supplying the air to the inside; and an air supply port 1912 for discharging the product generated in the cathode reaction from the inside. One example is the discharge port 1913 of water (any state including liquid phase or gas phase, or any state in which the states are mixed). It should be noted that this product contains water as a main component, but sometimes also contains formic acid, methyl formate, methanol (due to permeation described later) and the like.

The electrons move to the cathode 1906 through electrode wires 1905a and 1905b electrically connected to the electrodes 1904t and 1906t provided on the anode 1904 and the cathode 1906, and the protons move to the cathode 1906 through the membrane electrode assembly 1902. In addition, the cathode 1906 uses the electrons flowing through the external circuit to reduce oxygen supplied from the outside and protons transferred from the anode 1904 through the membrane electrode assembly 1902 to perform a reaction (cathode reaction) to produce water. In this way, the oxidation reaction proceeds at the anode 1904, and the reduction reaction proceeds at the cathode 1906, allowing electrons to flow to the electrode wires 1905a and 1905b to generate power.

In FIG. 34, in the membrane electrode assembly 1902 of the fuel cell main body 1900, for example, as the electrolyte membrane 1902b, DuPont's Nafion 117 (trade name) is used, and on one surface of the electrolyte membrane 1902b, the anode catalyst 1902a of the anode 1904 is used. , Formed on a carbon-based powder carrier dispersed and supported platinum and ruthenium, or platinum and ruthenium alloy material, on the other surface, as a cathode 1906 cathode catalyst 1902c, formed on a carbon-based carrier dispersed and supported platinum particles s material. The electrode and diffusion layers 1904d and 1906d made of carbon paper are closely attached to the anode catalyst 1902a and the cathode catalyst 1902c at both ends of the membrane electrode assembly 1902, and the anode side diaphragm 1904s and the cathode are interposed therebetween. One side diaphragm 1906s is fixed on the shell 1900h and assembled.

The cathode-side separator 1906s used the same as the cathode-side separator 1706s of the fourth embodiment, and as shown in FIGS. 26A and 26B, it is composed of a plate-shaped body of a non-conductive material that is flat in the thickness direction. The anode side diaphragm 1904s is the same as the anode side diaphragm 1704s of the fourth embodiment. As shown in FIG. 27, its main body is formed in the shape of a wave plate flat in the thickness direction, and the top line of the wave is along the fuel supply port 1919 connected to the anode. And the direction of the discharge port 1914.

As described above, in the fuel cell main body 1900, the discharge port 1914 is provided at a position higher than the fuel supply port 1919, so the liquid fuel flows into the anode passage (refer to 511 and 512 in FIG. 27), and the carbon dioxide generated by the anode reaction Ascend to the direction of the discharge port 1914 of the anode 1904 and discharge. As the carbon dioxide rises, the fuel in the anode also moves upward, and is discharged to the outside from the discharge port 1914 of the anode. If the fuel in the anode rises, the liquid fuel 120 stored in the fuel mixing tank 1932 flows into the anode 1904 from the fuel supply port of the anode. In this way, in the anode 1904, the carbon dioxide generated by the anode reaction is used as its thrust, and the liquid fuel is supplied and discharged. According to this, the liquid fuel 120 in the fuel mixing tank 1932 is convective.

It should be noted that in the present embodiment, the fuel supply port 1919 and the discharge port 1914 are opposed to each other, and depending on the arrangement direction of the fuel cell main body 1900, the two may also be exchanged. For example, when the arrangement in the direction shown in FIG. 34 is changed up and down, the port indicated by symbol 1919 is higher than the port indicated by symbol 1914, so liquid fuel is supplied from the port indicated by symbol 1914 (that is, it functions as a fuel supply port). Fuel is discharged from the port indicated by reference numeral 1919 (that is, it functions as a discharge port).

In addition, as the structure of the auxiliary machine for the fuel supply, there is a fuel mixing tank 1932 that stores and can supply a methanol aqueous solution to the anode 1904 as a liquid fuel. The fuel mixing tank 1932 stores a methanol aqueous solution whose concentration is lower than that of the liquid fuel stock solution stored in the fuel cell filling recovery unit 1920. In addition, the fuel supply pipe 1971 connected to the fuel supply port 1945 of the fuel cell filling recovery device 1920 communicates with the fuel intake port 1909 of the fuel mixing tank 1932.

The fuel mixing tank 1932 is integrally arranged with the fuel cell main body 1900, and the anode 1904 of the fuel cell main body 1900 is arranged so as to be immersed in the fuel mixing tank 1932. If the liquid fuel 120 is contained in the fuel mixing tank 1932, the anode 1904 is completely immersed in the liquid fuel 120. By disposing the anode 1904 in the fuel mixing tank 1932 in this way, the liquid fuel 120 is supplied to the inside of the anode 1904 through the fuel supply port 1919 in a state of being totally immersed in the liquid fuel 120 and discharged from the discharge port 1914. A detector 1939 for detecting the water level and fuel concentration of the liquid fuel 120 stored in the fuel mixing tank 1932 is provided in the fuel mixing tank 1932, and the information from the detector 1939 is transmitted to the control device 406.

In addition, the gas such as carbon dioxide generated by the anode reaction carried out in the anode 1904 flows into the fuel mixing tank 1932 through the discharge port 1914 of the anode 1904, but has an exhaust valve for discharging the gas thus introduced to the outside of the fuel mixing tank 1932 1911. It should be pointed out that the exhaust valve 1911 also functions as a suction part when the liquid fuel is initially injected into the fuel mixing tank 1932.

It should be noted that, instead of the fuel mixing tank 1932 and the fuel cell main body 1900 being integrally formed, and the anode 1904 is immersed in the fuel mixing tank 1932, as a modification, the two may be formed separately. At this time, it is preferable to provide a supply device for supplying liquid fuel from the fuel mixing tank 1932 to the anode 1904 as necessary.

Next, the fuel cell filling recovery device 1920 will be described. FIG. 35 is a schematic diagram showing the structure of a fuel cell reclaimer 1920 used in the fuel cell system 1910 of FIG. 33. The fuel cell filling and recovering device 1920 is shown in FIG. 35 and has: a container body 1940, a filling fuel storage space 1942, an effluent recovery space 1941, an effluent intake 1943, a water supply port 1944, a heating pipe 1921, a fuel supply connection 1954, connector 1953 for water recovery.

In addition, as shown in FIG. 36A, in the present embodiment, the container body 1940 has a guide rod 1956 provided across the filling fuel storage space 1942 and the effluent recovery space 1941. Parallel to the moving direction of the partition 1950, a guide rod 1956 is continuously provided from the discharge recovery space 1941 to the filling fuel storage space 1942. In order to cooperate with the guide rod 1956, a cutout is provided on the partition 1950. Although the thickness and number of the guide rods 1956 are not limited, if the volume efficiency of the fuel container is taken into consideration, it is preferable to reduce the occupancy rate. The partition 1950 moves in parallel along the guide rod 1956, so there is no need to have a given thickness as in the fifth embodiment, and it can be very thin.

In addition, on the separator 1950, a magnet 1955 used for the detection of the separator position based on the Hall element 1934 provided outside the fuel cell filling and recovering device 1920 is provided on a part of its periphery. The distance D that the partition 1950 can move is between the positions where the water recovery connector 1953 and the fuel supply connector 1954 can perform fuel supply and water recovery based on the fuel cartridge described later. Specifically, the upper limit position of the partition plate 1950 is in the vicinity of the lower side of the water supply port 1944, below the lower end of the heat radiation pipe 1921. The lower end position is a position near the upper side of the fuel supply connector 1954, where fuel can be supplied to the fuel storage space 1942 for filling.

In the fuel cell filling recovery unit 1920, in order to replenish fuel and recover water, a water recovery connector 1953 is installed in the exhaust recovery space 1941, and a fuel replenishing connector 1954 is installed in the filling fuel storage space 1942. Both the water recovery connector 1953 and the fuel supply connector 1954 have a leak prevention mechanism. The water recovery connector 1953 and the fuel supply connector 1954 are connected to the regenerator 3900 as shown in FIG. 37.

FIG. 37 shows a connection configuration diagram of the fuel cell filling recovery unit 1920 and the regenerator 3900 during regeneration. The same as the regenerator 3300 shown in FIG. 8, the regenerator 3900 has a regenerator housing 3910, with a piston 3920 disposed in the regenerator housing 3910 and capable of moving along the axial direction 3910a of the regenerator housing 3910; and The fuel supply connector 1953 and the water recovery connector 1953 on the fuel cell filling recovery unit 1920 are fitted with the above-mentioned plug parts 3935 and 3936, respectively.

The piston 3920 has: a partition 3921 that divides the regenerator housing 3910 into an exhaust accommodating part 3911 and a fuel supply part 3912; is protrudingly provided on the partition 3921, extends along the axial direction 3910a, and penetrates the regenerator housing 3910, reach the outside pole 3922. The regenerating operation of the fuel cell filling and recovering device 1920 using the regenerator 3900 having the above structure is the same as that of the second embodiment, so the description is omitted.

Next, the operation of each component device when generating power in the fuel cell system 1910 of FIG. 33 will be described.

First, in the fuel cell system 1910 shown in FIG. 33, the anode 1904 is immersed in the fuel mixing tank 1932, and fuel exists in the anode 1904. Therefore, if the air supply pump 1939 is driven to supply oxygen to the cathode 1906, power generation starts.

The inside of the cathode is pressurized by the air supply pump 1939, and the effluent containing water and air generated by the reaction at the cathode 1906 is sent to the effluent supply pipe 1938 through the exhaust port 1913, and is supplied to the fuel cell filling recovery device 1920.

Due to power generation, water and methanol are consumed, and if the remaining amount of fuel in the fuel mixing tank 1932 decreases, the detector 1939 that detects the liquid level and the fuel concentration of the fuel mixing tank sends this signal to the control device 406 and receives the signal. The device 406 adjusts the opening degree of the fuel adjusting valve 1960 and the water valve 1933, and supplies the necessary amount of water and methanol to the fuel mixing tank 1932. Water and methanol are respectively supplied from the filling fuel storage space 1942 and the exhaust material recovery space 1941 of the fuel cell filling recovery unit 1920. At this time, depending on whether the fuel concentration in the fuel mixing tank 1932 detected by the detector 1939 is higher or lower than the reference concentration value, the opening degree of the fuel regulating valve 1960 and the water valve 1933 can be adjusted to change the supply to the fuel mixing tank. The ratio of water to methanol.

In addition, when the liquid level of the fuel mixing tank is lower than the upper end of the anode, if power is generated in this state, fuel may not be supplied to the entire anode, so the fuel cell may be damaged. Therefore, if a signal is sent from the liquid level sensor to the control device that the liquid level is lower than a given water level, for example, the discharge port 1914, the water valve 1933 is first opened, and water is preferentially supplied until the given level. When there is no water on the way, or the concentration is too diluted, open the fuel valve as necessary and supply it with fuel.

The specific material balance of the fuel cell system 1910 of FIG. 33 is as follows. An example of the material balance of the fuel cell system 1910 of FIG. 33 under ideal conditions is shown in FIG. 38. It should be noted that the membrane electrode assembly 1902 of the fuel cell system 1910 is formed to basically not pass methanol or water, but so-called permeation occurs in which a small amount of methanol or water passes. However, in the following material balance description, in order to make the understanding of the description easy, the description will be made assuming that no permeation occurs in the membrane electrode assembly 1902.

In the fuel cell system 1910, in the filling fuel storage space 1942 of the fuel cell filling recovery device 1920, a methanol aqueous solution with a concentration of 68% by weight is used as a liquid fuel stock solution, and 100 ml is contained. That is, it contains 57.6g (72.6ml) of methanol and 27.3g (27.4ml) of water. The liquid fuel stock solution is diluted by the water supplied from the effluent recovery space 1941 of the fuel cell filling recovery device, and a methanol aqueous solution with a concentration of 6.5% by weight is supplied to the anode 1904.

In this embodiment, the anode 1904 is arranged inside the fuel mixing tank 1932. However, for ease of understanding, it is assumed that the fuel and water from the fuel cell filling and recovering device 1920 are supplied to the virtual fuel mixing tank, fully stirred, and When a container storing a methanol aqueous solution with a concentration of 6.5 wt% supplies a necessary amount to the anode. In fact, not only the necessary amount of fuel in the fuel mixing tank is supplied to the anode, as described above, the anode is immersed in the liquid fuel in the fuel mixing tank, and the liquid fuel in the fuel mixing tank is used to perform the anode reaction. The virtual fuel mixing tank is 100ml, the same volume as the filling recovery device for fuel cells, and contains 6.4g (8.1ml) of methanol and 91.8g (91.9ml) of water.

If a 6.5 wt% methanol aqueous solution is supplied to the anode to start power generation, the methanol stored in the fuel mixing tank will be consumed. In the anode 1904, 6.4 g (8.1 ml) of methanol and 3.6 g (3.6 ml) of water in the liquid fuel are consumed, and at the cathode 1906, 10.8 g (10.8 ml) of water is produced.

At this time, it is necessary to supply the methanol aqueous solution that is consumed and reduced at the anode 1904, so 11.1 ml (8.1 ml of methanol, 3.0 ml of water) of liquid fuel stock solution of 6.4 g (8.1 ml) of methanol is supplied from the fuel cell reclaimer 1920. 0.6ml of the water consumed at the anode and the shortage of the liquid fuel stock solution is used. The water produced at the cathode 1906 is supplied to the fuel mixing tank (actually, 10.8ml of water produced at the cathode is taken into the fuel cell reclaimer In the effluent recovery space, 0.6 ml of water is supplied to the anode through the water supply port 1944 and the water supply pipe 1972).

Due to the supply of fuel, the amount of the liquid fuel stock solution stored in the filling fuel storage space 1942 of the fuel cell filling and recovering device 1920 after the power generation is reduced to 88.9 ml. In addition, 10.2 ml of water is stored in the effluent recovery space, and a total of 99.1 ml of water and methanol are stored in the filling recovery device for fuel cells.

In addition, if electricity is repeatedly generated and the supplied methanol is consumed at the anode 1904, 6.4g (8.1ml) of methanol in the liquid fuel and 3.6g (3.6ml) of water in the liquid fuel are also consumed in the anode 1904, and 10.8g ( 10.8ml) of water. 11.1 ml (8.1 ml of methanol, 3.0 ml of water) of the consumed portion of methanol was supplied from the liquid fuel stock solution of the fuel cell filling recovery device. Using the water generated in the cathode 1906, the difference between 3.6 ml of water consumed in the anode and the amount of water supplied from the fuel storage space 1942 for filling is supplied to the anode 1904.

As a result, at the end of the second methanol supply, the amount of liquid fuel stock solution stored in the filling fuel storage space 1942 of the fuel cell filling and recovering device became 77.8 ml, and the amount of water stored in the effluent recovery space was 20.4 ml. Therefore, the total liquid volume of the fuel cell filling and recovering device becomes 98.2 ml. In the fuel cell filling and recovering device 1920, all the water generated at the cathode is not released to the outside and can be recovered in the system.

In this way, by repeating power generation, liquid fuel replenishment, and recovery of produced water, the amount of liquid fuel stock solution 100 contained in the filling fuel storage space 1942 of the fuel cell filling and recovering device 1920 gradually decreases, and is stored in the effluent recovery The amount of water 110 in the space 1941 increases. The separator 1950 of the fuel cell filling and recovering device 100 moves to the side of the filling fuel storage space with the decrease in the amount of liquid fuel stock and the increase in the amount of water stored in the exhaust recovery space 1941. Pressurize. The air discharged from the cathode 1906 flows into the effluent recovery space 1941 of the fuel cell filling and recovering device together with water. Therefore, due to the air pressure, the pressure of the effluent recovery space 1941 of the fuel cell filling and recovering device is increased and serves as a pressing separator. The force of the force. It should be pointed out that when the pressure in the discharge recovery space 1941 is too high, the pressure is automatically adjusted to a given value by opening the pressure regulating valve 1962 provided on the outer wall of the discharge recovery space.

It should be pointed out that the Hall element 1934 detects the position of the magnet 1955 mounted on the partition 1950, detects the position of the partition 1950, and sends the information to the control device 406 to calculate the filling fuel storage space 1942. The residual amount of fuel. The remaining amount of fuel information is displayed on the electronic device equipped with the fuel cell system, and can be used to display the replacement time of the fuel cell refill recovery device.

In the above description, for ease of understanding, after all the methanol supplied in the initial state (in the description, stored in the fuel mixing tank) is consumed, methanol is replenished from the fuel cell filling recovery device, but in actual use, The supply of methanol is continuously performed. Therefore, in this embodiment, similar to the fuel cell system 1 of the first embodiment, as shown in FIG. 39, power generation can be continuously performed until the liquid fuel stock solution 110 stored in the fuel cell filling and recovering device disappears, even if all The total volume of the fuel cell filling recovery device 1920 is not increased by recovering the water generated in the power generation. Even if a tank for recovering water is not prepared separately, the fuel can be filled up to the allowable volume of the fuel cell filling recovery device.

In addition, the water and air stored in the fuel cell filling and recovering device move the separator 1950 to the side of the filling fuel storage space 1942 and eject the fuel stored in the fuel cell filling and recovering device 1920, so it serves as a secondary fuel cell. The filling recovery device is a power source for transporting liquid fuel, and there is no need to install a pump, etc., which can reduce the self-consumption power of the fuel cell system.

As described above, the fuel cell system of this embodiment does not discharge the water generated from the cathode to the outside, but stores it in the fuel cell filling and recovering device, and uses it for the transportation of fuel and water for fuel dilution, so there is no need to install it. The pump used to transport them. Therefore, the power consumed by the auxiliary machine is reduced, and the output efficiency of the fuel cell system can be improved. In addition, the remaining amount of the fuel cell can be easily calculated, and the user of the electronic device can be notified of the replacement time of the fuel cell refill recovery device.

In addition, the fuel cell system of the fifth or sixth embodiment is compact and does not release moisture to the outside, so it is suitable for portable electronic equipment.

In addition, in the fuel filling and recovering device of this embodiment, instead of partitions divided into the fuel storage space and the exhaust recovery space, for example, a flexible polymer film may be used to divide the fuel storage space and the exhaust recovery space, and the same Operation, but because the polymer film is not resistant to temperature and pressure, the possibility of deformation or damage is high.

It should be noted that the present invention is not limited to the above-mentioned embodiments, and can be implemented in various forms.

In addition, by appropriately combining any of the above-described embodiments, the respective effects can be produced.

Japanese Patent Application No. 2003-173150 filed on June 18, 2003, Japanese Patent Application No. 2003-173405 filed on June 18, 2003, and Japanese Patent Application No. 2003-173446 filed on June 18, 2003 , And Japanese Patent Application No. 2004-49953 filed on February 25, 2004, including the specification, claims, drawings, and abstracts, all of which are included in the present invention by reference.

The present invention has been fully described in connection with the preferred embodiments with reference to the drawings. However, it should be clear to those skilled in the art that various modifications or corrections should be construed as being included as long as they do not depart from the scope of the present invention in the appended claims. among them.