JP2007214046A - Fuel cell system and its operation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell system in which fuel concentration can be stabilized by using a clathrating technology in a circulating type fuel cell system, and its operating method. <P>SOLUTION: The fuel cell system is provided with the fuel cell 104, a aqueous solution tank 130 to hold a methanol aqueous solution to be supplied to the fuel cell 104, a fuel taking in/discharge member 208 composed of a host compound to hold liquid methanol 210 contained in the methanol aqueous solution when contacted with the methanol aqueous solution of higher concentration than a prescribed value and to discharge the liquid methanol 210 when contacted with the methanol aqueous solution of lower concentration than the prescribed value, and a control means to control inflow and outflow of the fuel taking in/discharge member 208 to the methanol aqueous solution held in the aqueous solution tank 130. By contacting the fuel taking in/discharge member 208 with the methanol aqueous solution in the aqueous solution tank 130, the concentration of the methanol aqueous solution existing in the aqueous solution tank 130 is adjusted. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fuel cell system and a method for operating the fuel cell system, and more particularly to a fuel cell system for supplying an aqueous fuel solution directly to the fuel cell and a method for operating the fuel cell system.

  A fuel cell system that directly supplies an aqueous fuel solution to a fuel cell is operated while detecting the fuel concentration (concentration of the aqueous fuel solution) with an ultrasonic sensor or the like and controlling the concentration so that the fuel concentration becomes constant.

  However, the ultrasonic sensor cannot accurately detect the fuel concentration when bubbles are attached to the sensor surface. On the other hand, concentration detection is also performed by an electrochemical sensor, but this sensor cannot be used because the detection accuracy is not high in a low temperature region.

Further, Patent Document 1 discloses a technique for replenishing fuel by putting a clathrate compound into a single-use container such as a cartridge instead of a circulation type and gradually releasing the fuel.
JP 2005-203335 A

  However, it is difficult to realize such a system with a fuel cell system of a type in which an aqueous fuel solution is circulated and driven continuously for a relatively long time because a disposable cartridge cannot be sufficiently replenished.

  SUMMARY OF THE INVENTION Therefore, a main object of the present invention is to provide a fuel cell system and a method for operating the fuel cell system that can stabilize the fuel concentration by using the inclusion compound technique in the circulation type fuel cell system.

  In order to achieve the above object, a fuel cell system according to claim 1 is a fuel cell system that circulates and uses an aqueous fuel solution, and is supplied to a fuel cell and a fuel cell that generate electric energy by an electrochemical reaction. A first aqueous solution holding means for holding the aqueous fuel solution, which takes in the liquid fuel contained in the aqueous fuel solution when it comes into contact with the aqueous fuel solution having a concentration higher than a predetermined value; A fuel intake / release member made of the host compound to be released, and a control means for controlling the fuel intake / release member to / from the aqueous fuel solution held by the first aqueous solution holding means.

  The fuel cell system according to claim 2 is the fuel cell system according to claim 1, wherein the control means is a fuel replenishing means for replenishing the first aqueous solution holding means with fuel having a concentration equal to or higher than the aqueous fuel solution, and the first aqueous solution. Water supply means for supplying water to the holding means, and operations of the fuel supply means and the water supply means are controlled in order to control the fuel intake / release member to / from the fuel aqueous solution held by the first aqueous solution holding means. An operation control unit is included.

  The fuel cell system according to claim 3 is the fuel cell system according to claim 1, wherein the control means is a second aqueous solution holding means for holding the aqueous fuel solution, and the fuel from the first aqueous solution holding means to the second aqueous solution holding means. First supply means for supplying an aqueous solution, second supply means for supplying an aqueous fuel solution from the second aqueous solution holding means to the first aqueous solution holding means, and fuel intake / release into the aqueous fuel solution held by the first aqueous solution holding means An operation control unit for controlling operations of the first supply unit and the second supply unit in order to control the entry / exit of the member is characterized.

  The fuel cell system according to claim 4 is the fuel cell system according to claim 3, wherein water holding means for holding water discharged from the fuel cell, and water held in the water holding means are held in the first aqueous solution. The water supply means also serves as the second aqueous solution holding means, the water supply means serves also as the first supply means or the second supply means, and the operation control unit is held in the first aqueous solution holding means. The operation of the water supply means is controlled in order to control the entry / exit of the fuel take-in / release member into the aqueous fuel solution.

  The fuel cell system according to claim 5 is the fuel cell system according to claim 1, wherein the control means includes a holding portion that holds the fuel intake / release member, a support portion that supports the holding portion movably, and An operation control unit that controls the operation of the support unit in order to control the fuel intake / release member to / from the fuel aqueous solution held by the first aqueous solution holding unit is included.

  The fuel cell system according to claim 6 is the fuel cell system according to claim 1, wherein the first aqueous solution holding means is replenished with fuel having a concentration equal to or higher than the aqueous fuel solution, and the fuel intake / release member. And a holding portion that is disposed in the first aqueous solution holding means and is supplied with fuel.

  A transportation device according to a seventh aspect includes the fuel cell system according to any one of the first to sixth aspects.

  The operation method of the fuel cell system according to claim 8 is an operation method of the fuel cell system that circulates and uses the aqueous fuel solution, the aqueous fuel solution supplied to the fuel cell is held by the first aqueous solution holding means, and the predetermined value A fuel intake / release member comprising a host compound that takes in liquid fuel contained in the aqueous fuel solution when it comes into contact with a higher concentration aqueous fuel solution and releases the liquid fuel when brought into contact with the aqueous fuel solution at a concentration lower than a predetermined value. It arrange | positions in 1 aqueous solution holding means, and adjusts the density | concentration of the fuel aqueous solution which exists in a 1st aqueous solution holding means by making a fuel intake / release member and a fuel aqueous solution contact.

  The fuel cell system operating method according to claim 9 is the fuel cell system operating method according to claim 8, wherein the fuel intake / release member is changed by changing a liquid level of the aqueous fuel solution in the first aqueous solution holding means. And contact with the aqueous fuel solution.

  The fuel cell system operating method according to claim 10 is the fuel cell system operating method according to claim 8, wherein the fuel supplied to the first aqueous solution holding means is a fuel having a concentration equal to or higher than the aqueous fuel solution. The amount of the fuel aqueous solution existing in the first aqueous solution holding means is adjusted by controlling the replenishment amount to the first aqueous solution holding means to control the contact between the fuel intake / release member and the aqueous fuel solution. To do.

  An operation method of the fuel cell system according to claim 11 is the operation method of the fuel cell system according to claim 8, wherein the supply amount of the fuel aqueous solution from the first aqueous solution holding means to the second aqueous solution holding means and the second aqueous solution By controlling the supply amount of the aqueous fuel solution from the holding means to the first aqueous solution holding means, the amount of the aqueous fuel solution existing in the first aqueous solution holding means is adjusted, and the contact between the fuel intake / release member and the aqueous fuel solution is adjusted. It is characterized by controlling.

  The fuel cell system operating method according to claim 12 is the fuel cell system operating method according to claim 8, wherein the fuel intake / release member is movably held and the fuel intake / release member is moved. Thus, the contact between the fuel intake / release member and the aqueous fuel solution in the first aqueous solution holding means is controlled.

  The fuel cell system operating method according to claim 13 is the fuel cell system operating method according to claim 8, wherein the fuel intake / release member is made to hold the liquid fuel after the start instruction of the fuel cell. It is characterized by.

  The fuel cell system operation method according to claim 14 is the fuel cell system operation method according to claim 8, wherein after the fuel cell stop instruction is given, the fuel intake / release member holds the liquid fuel. It is characterized by.

  If the inclusion compounding technique is used, when the fuel intake / release member made of the host compound comes into contact with the aqueous fuel solution, the liquid fuel is held or released according to the concentration of the aqueous fuel solution. In the fuel cell system according to claim 1, using this technique, the fuel intake / release member is inserted into the fuel aqueous solution held by the first aqueous solution holding means, and the fuel intake / release member and the aqueous fuel solution are brought into contact with each other. As a result, the concentration of the aqueous fuel solution can be made constant. In a fuel cell system of the type that circulates and uses an aqueous fuel solution, the concentration of the aqueous fuel solution can be obtained without concentration control by inserting a fuel intake / release member into the first aqueous solution holding means whenever concentration control is required. Can be stabilized. Also, the concentration can be changed by removing the fuel intake / release member from the aqueous fuel solution. The same applies to the operation method of the fuel cell system according to claim 8.

  In the fuel cell system according to claim 2, the amount of the fuel aqueous solution in the first aqueous solution holding means is easily adjusted by controlling the replenishment amount of fuel and water to the first aqueous solution holding means. The fuel intake / release member can be easily controlled in and out of the aqueous fuel solution held by the holding means. The same applies to the operation method of the fuel cell system according to claim 10.

  In the fuel cell system according to claim 3, by providing the second aqueous solution holding means for enabling the withdrawal or return of the aqueous fuel solution, the amount of liquid in the first aqueous solution holding means can be quickly changed, It is possible to quickly control the fuel intake / release member to / from the fuel aqueous solution held by the first aqueous solution holding means. The same applies to the operation method of the fuel cell system according to claim 11.

  In the fuel cell system according to claim 4, the amount of liquid in the first aqueous solution holding means can be changed with a simple configuration without separately providing the first aqueous solution holding means.

  In the fuel cell system according to claim 5, by changing the position of the holding portion and thus the fuel intake / release member, the fuel intake / release member is moved into and out of the fuel aqueous solution held by the first aqueous solution holding means. Easy to control. When the capacity of the first aqueous solution holding means is large and it takes time to diffuse the liquid fuel, the fuel aqueous solution close to the target concentration can be obtained by moving the fuel intake / release member near the aqueous solution outlet of the first aqueous solution holding means. It can be supplied to the anode of the fuel cell. The same applies to the operation method of the fuel cell system according to claim 12.

  In the fuel cell system according to claim 6, by arranging the fuel intake / release member in the holding portion, a high concentration aqueous fuel solution can be easily supplied to the fuel intake / release member. -Liquid fuel can be quickly held by the discharge member.

  The present invention is suitably used when the fuel cell system is mounted on a transportation device as described in claim 7.

  In the operation method of the fuel cell system according to claim 9, the contact between the fuel intake / release member and the aqueous fuel solution can be easily controlled by changing the liquid level of the aqueous fuel solution in the first aqueous solution holding means. it can.

  In the operation method of the fuel cell system according to claim 13, since the liquid fuel can be held by the fuel intake / release member immediately before the fuel cell is supplied to the fuel cell, the liquid fuel is not vaporized and evaporated. Fuel efficiency can be improved.

  In the operation method of the fuel cell system according to claim 14, the next start of the fuel cell can be smoothly performed by holding the liquid fuel in the fuel intake / release member after the stop instruction of the fuel cell. .

  According to the present invention, it is possible to stabilize the fuel concentration using the inclusion compounding technique in the circulation type fuel cell system.

  Embodiments of the present invention will be described below with reference to the drawings. Here, a case where the fuel cell system 100 of the present invention is mounted on a motorcycle 10 which is an example of a transportation device will be described.

  First, the motorcycle 10 will be described. Left and right, front and rear, and top and bottom in the embodiment of the present invention mean left and right, front and back, and top and bottom, based on a state where the driver is seated on the seat of the motorcycle 10 toward the handle 24 thereof.

  1 to 7, the motorcycle 10 includes a vehicle body 11, and the vehicle body 11 has a vehicle body frame 12. The vehicle body frame 12 includes a head pipe 14, a front frame 16 having an I-shaped longitudinal section extending obliquely downward from the head pipe 14, and a rear frame connected to a rear end portion of the front frame 16 and rising obliquely upward rearward. 18 and a seat rail 20 attached to the upper end of the rear frame 18. The rear end portion of the front frame 16 is connected to a position slightly closer to the lower end portion than the center portion of the rear frame 18, and the front frame 16 and the rear frame 18 as a whole have a substantially Y shape in side view.

  The front frame 16 has a plate-like member 16a having a width in the up-down direction, extending obliquely downward to the rear and orthogonal to the left-right direction, and formed at the upper and lower edges of the plate-like member 16a, respectively, and to the rear. Flange portions 16b and 16c extending obliquely downward and having a width in the left-right direction, reinforcing ribs 16d projecting on both surfaces of the plate-like member 16a, and the rear frame 18 are connected to each other by, for example, bolts provided at the rear end portion. Connecting portion 16e. The reinforcing rib 16d partitions both surfaces of the plate-like member 16a together with the flange portions 16b and 16c to form a storage space for storing components of the fuel cell system 100 described later.

  On the other hand, the rear frame 18 extends rearward and obliquely upward, has a width in the front-rear direction, and is disposed so as to sandwich the connecting portion 16e of the front frame 16, and the plate-shaped members 18a and 18b. And a plate-like member (not shown) for connecting the two.

  As shown in FIG. 1, a steering shaft 22 for changing the vehicle body direction is rotatably inserted into the head pipe 14. A handle support portion 26 to which a handle 24 is fixed is attached to the upper end of the steering shaft 22, and grips 28 are attached to both ends of the handle 24. The right grip 28 constitutes a rotatable throttle grip.

  A display operation unit 30 is disposed in front of the handle 24 of the handle support unit 26. The display operation unit 30 includes a meter 30a for measuring and displaying various data of an electric motor 60 (described later), a display unit 30b configured by, for example, a liquid crystal display for providing various information such as a running state, and various information input. The input unit 30c and the like are integrated. A headlamp 32 is fixed below the display operation section 30 in the handle support section 26, and flasher lamps 34 are provided on both the left and right sides of the headlamp 32.

  A pair of left and right front forks 36 are attached to the lower end of the steering shaft 22, and a front wheel 38 is attached to the lower end of each front fork 36 via a front axle 40. The front wheel 38 is rotatably supported by the front axle 40 while being buffered and suspended by the front fork 36.

  On the other hand, a frame-like seat rail 20 is attached to the rear end portion of the rear frame 18. The seat rail 20 is fixed to the upper end portion of the rear frame 18 by welding, for example, and is disposed substantially in the front-rear direction. A seat (not shown) is provided on the seat rail 20 so as to be freely opened and closed. A mounting bracket 42 is fixed to the rear end portion of the seat rail 20, and a tail lamp 44 and a pair of left and right flasher lamps 46 are mounted on the mounting bracket 42, respectively.

  A swing arm (rear arm) 48 is swingably supported at the lower end portion of the rear frame 18 via a pivot shaft 50, and an electric motor 60 (described later) is provided at a rear end portion 48a of the swing arm 48. A rear wheel 52, which is a drive wheel, is rotatably supported, and the swing arm 48 and the rear wheel 52 are buffered and suspended from the rear frame 18 by a rear cushion (not shown).

  Further, a footrest mounting bar 54 is fixed to the front side of the lower end portion of the rear frame 18 so as to protrude from the rear frame 18 in the left-right direction, and a footrest (not shown) is mounted on the footrest mounting bar 54. Behind the footrest mounting bar 54, a main stand 56 is rotatably supported by a swing arm 48, and the main stand 56 is urged toward the closing side by a return spring 58.

  In this embodiment, the swing arm 48 is connected to the rear wheel 52, for example, an axial gap type electric motor 60 for rotating the rear wheel 52, and a drive unit 62 electrically connected to the electric motor 60. And built-in. Referring also to FIG. 11, drive unit 62 includes a controller 64 for controlling the rotational drive of electric motor 60 and a storage amount detector 65 for detecting a storage amount of secondary battery 134 (described later). .

  A fuel cell system 100 is attached to the vehicle body 11 of the motorcycle 10 along the vehicle body frame 12. The fuel cell system 100 generates electrical energy for driving the electric motor 60 and other components.

Hereinafter, the fuel cell system 100 will be described.
The fuel cell system 100 is a direct methanol fuel cell system that directly uses methanol (aqueous methanol solution) for power generation without reforming.

  The fuel cell system 100 includes a fuel cell stack (hereinafter simply referred to as a cell stack) 102 disposed below the front frame 16.

  As shown in FIGS. 8 and 9, the cell stack 102 sandwiches a separator 106 with a fuel cell (fuel cell) 104 that can generate electric energy by an electrochemical reaction between hydrogen ions based on methanol and oxygen. A plurality of layers are stacked. Each fuel cell 104 constituting the cell stack 102 includes an electrolyte membrane 104a made of a solid polymer membrane, an anode (fuel electrode) 104b and a cathode (air electrode) 104c facing each other with the electrolyte membrane 104a interposed therebetween. including. Each of the anode 104b and the cathode 104c includes a platinum catalyst layer provided on the electrolyte membrane 104a side.

  As shown in FIG. 4 and the like, the cell stack 102 is placed on a skid 108, and the skid 108 is supported by a stay stack 110 that is suspended from a flange portion 16 c of the front frame 16.

  As shown in FIG. 6, an aqueous solution radiator 112 and a gas-liquid separation radiator 114 are disposed below the front frame 16 and above the cell stack 102. The radiators 112 and 114 are integrally formed, and have a plurality of plate-like fins (not shown) whose front surfaces are disposed slightly forward of the vehicle and are orthogonal to the front surfaces. Such radiators 112 and 114 can sufficiently receive wind during traveling.

  As shown in FIG. 6 and the like, the radiator 112 includes a radiator pipe 116 that is formed to pivot. The radiator pipe 116 is formed as a single continuous pipe from the inlet 118a (see FIG. 5) to the outlet 118b (see FIG. 3) by welding a straight pipe made of stainless steel or the like and a U-shaped joint pipe. Is formed. A radiator cooling fan 120 is provided on the back side of the radiator 112 so as to face the radiator pipe 116.

  Similarly, the radiator 114 includes two radiator pipes 122 formed to meander. Each radiator pipe 122 is a continuous pipe from the inlet 124a (see FIG. 3) to the outlet 124b (see FIG. 3) by welding a straight pipe made of stainless steel or the like and a U-shaped joint pipe. Is formed. A radiator cooling fan 126 is provided on the back surface side of the radiator 114 so as to face the radiator pipe 122.

  1 to 7 and mainly referring to FIG. 3, a fuel tank 128, an aqueous solution tank 130, and a water tank 132 are arranged in order from the top on the rear side of the connecting portion 16 e of the front frame 16. The fuel tank 128, the aqueous solution tank 130, and the water tank 132 are obtained by, for example, PE (polyethylene) blow molding.

  The fuel tank 128 is disposed below the seat rail 20 and is attached to the rear end portion of the seat rail 20. The fuel tank 128 contains methanol fuel (high-concentration aqueous methanol solution) with a high concentration (for example, containing about 56 wt% of methanol) that becomes a fuel for the electrochemical reaction of the cell stack 102. The fuel tank 128 has a lid 128a on its upper surface, and the lid 128a is removed to supply methanol fuel.

  The aqueous solution tank 130 is provided below the fuel tank 128 and attached to the rear frame 18. The aqueous solution tank 130 contains an aqueous methanol solution obtained by diluting the methanol fuel from the fuel tank 128 to a concentration suitable for the electrochemical reaction of the cell stack 102 (for example, containing about 3 wt% of methanol). That is, the aqueous solution tank 130 contains an aqueous methanol solution to be sent out toward the cell stack 102 by an aqueous solution pump 146 (described later). The aqueous methanol solution corresponds to the aqueous fuel solution.

  A level sensor 129 is attached to the fuel tank 128 to detect the level of the methanol fuel level in the fuel tank 128. A level sensor 131 is attached to the aqueous solution tank 130 to detect the level of the aqueous methanol solution in the aqueous solution tank 130. By detecting the liquid level height with the level sensors 129 and 131, the amount of liquid in the tank can be detected. The liquid level in the aqueous solution tank 130 is controlled within a range indicated by A in FIG. 4 based on the output of the level sensor 131, for example.

  The water tank 132 is disposed between the plate-like members 18 a and 18 b of the rear frame 18 and on the rear side of the cell stack 102. A level sensor 133 is attached to the water tank 132 and the height of the water surface in the water tank 132 is detected.

  A secondary battery 134 is provided on the front side of the fuel tank 128 and on the upper side of the flange portion 16 b of the front frame 16. The secondary battery 134 is disposed on the upper surface of a plate-like member (not shown) of the rear frame 18. The secondary battery 134 stores the electrical energy generated by the cell stack 102 and supplies the electrical energy to the corresponding electrical component in accordance with a command from a controller 156 (described later). For example, the secondary battery 134 supplies electric energy to the auxiliary machines and the drive unit 62.

A fuel pump 136 is disposed above the secondary battery 134 and below the seat rail 20. A catch tank 140 is disposed above the aqueous solution tank 130.
The catch tank 140 is provided with a lid 140a on the upper surface thereof. For example, in a state where the fuel cell system 100 has never been activated (the aqueous solution tank 130 is empty), the aqueous methanol solution is supplied by removing the lid 140a. The catch tank 140 is obtained by PE (polyethylene) blow molding, for example.

  An air filter 142 for removing foreign substances such as dust contained in the gas is disposed in a space surrounded by the front frame 16, the cell stack 102, and the radiators 112 and 114. On the side, an aqueous solution filter 144 is arranged.

  As shown in FIG. 4, an aqueous solution pump 146 and an air pump 148 are stored in the storage space on the left side of the front frame 16. An air chamber 150 is disposed on the left side of the air pump 148. By driving the aqueous solution pump 146, an aqueous methanol solution is sent out toward the cell stack 102.

  Further, as shown in FIG. 5, a main switch 152, a DC-DC converter 154, a controller 156, a rust prevention valve 158, and a water pump 160 are arranged in order from the front in the storage space on the right side of the front frame 16. The main switch 152 is provided so as to penetrate the storage space of the front frame 16 from the right side to the left side. A horn 162 is provided on the front surface of the cell stack 102. The DC-DC converter 154 converts the voltage from 24V to 12V, and the fans 120 and 126 are driven by the converted 12V voltage.

The piping of the fuel cell system 100 arranged in this way will be described with reference to FIGS. 4 to 7 and FIG.
The fuel tank 128 and the fuel pump 136 are connected by a pipe P1, and the fuel pump 136 and the aqueous solution tank 130 are connected by a pipe P2. The pipe P1 connects the lower end of the left side of the fuel tank 128 and the lower end of the left side of the fuel pump 136, and the pipe P2 connects the lower end of the left side of the fuel pump 136 and the upper right side of the aqueous solution tank 130. By driving the fuel pump 136, the methanol fuel in the fuel tank 128 is supplied to the aqueous solution tank 130 through the pipes P1 and P2.

  The aqueous solution tank 130 and the aqueous solution pump 146 are communicated by a pipe P3, the aqueous solution pump 146 and the aqueous solution filter 144 are communicated by a pipe P4, and the aqueous solution filter 144 and the cell stack 102 are communicated by a pipe P5. The pipe P3 connects the lower left side corner of the aqueous solution tank 130 and the rear portion of the aqueous solution pump 146, the pipe P4 connects the rear portion of the aqueous solution pump 146 and the left side surface of the aqueous solution filter 144, and the pipe P5 connects the aqueous solution filter 144. The right side is connected to the anode inlet I1 located at the lower right corner of the front surface of the cell stack 102. By driving the aqueous solution pump 146, the aqueous methanol solution from the aqueous solution tank 130 is sent from the pipe P3 side to the pipe P4 side, and after impurities are removed by the aqueous solution filter 144, the aqueous solution pump 146 enters the cell stack 102 via the pipe P5. Given. In this embodiment, pipes P4 and P5 constitute pipes for guiding the aqueous methanol solution sent out by the aqueous solution pump 146 to each fuel cell 104 of the cell stack 102.

  The cell stack 102 and the aqueous solution radiator 112 are connected by a pipe P6, and the radiator 112 and the aqueous solution tank 130 are connected by a pipe P7. The pipe P6 connects the anode outlet I2 located at the upper left corner of the rear surface of the cell stack 102 and the inlet 118a (see FIG. 5) of the radiator pipe 116 drawn from the lower right end of the radiator 112, and the pipe P7 is connected to the radiator 112. The outlet 118b of the radiator pipe 116 (see FIG. 3) drawn from a position slightly closer to the center from the lower left end of the lower surface of the aqueous solution tank 130 is connected to the upper left corner of the aqueous solution tank 130. The unreacted aqueous methanol solution and carbon dioxide discharged from the cell stack 102 are supplied to the radiator 112 via the pipe P6, the temperature is lowered, and returned to the aqueous solution tank 130 via the pipe P7. As a result, the temperature of the aqueous methanol solution in the aqueous solution tank 130 can be lowered.

  The pipes P1 to P7 described above mainly serve as fuel flow paths.

  Further, the air filter 142 and the air chamber 150 are communicated by a pipe P8, the air chamber 150 and the air pump 148 are communicated by a pipe P9, and the air pump 148 and the rust prevention valve 158 are connected by a pipe P10 and are used for rust prevention. The valve 158 and the cell stack 102 are connected by a pipe P11. The pipe P8 connects the rear part of the air filter 142 and a position slightly ahead of the center part of the air chamber 150, and the pipe P9 connects the lower side of the center part of the air chamber 150 and the rear part of the air pump 148. P10 connects the air pump 148 located on the left side of the plate member 16a of the front frame 16 and the rust prevention valve 158 located on the right side of the plate member 16a, and the pipe P11 is connected to the rust prevention valve 158 and the cell stack 102. To the cathode inlet I3 located at the upper right end of the rear surface. When the fuel cell system 100 is operated, the rust prevention valve 158 is opened, and the air pump 148 is driven in this state, whereby oxygen-containing air is sucked from the outside. The sucked air is purified by the air filter 142 and then flows into the air pump 148 through the pipe P8, the air chamber 150 and the pipe P9, and further, the cell is passed through the pipe P10, the rust prevention valve 158 and the pipe P11. Is provided to the stack 102. The rust prevention valve 158 is closed when the fuel cell system 100 is stopped, and prevents the backflow of water vapor to the air pump 148 and prevents the air pump 148 from rusting.

  The cell stack 102 and the radiator 114 for gas-liquid separation are communicated with each other by two pipes P12. The radiator 114 and the water tank 132 are communicated by two pipes P13, and the water tank 132 is connected to a pipe (exhaust pipe) P14. Is provided. Each pipe P12 connects a cathode outlet I4 located at the lower left corner of the front surface of the cell stack 102 and an inlet 124a (see FIG. 3) of each radiator pipe 122 drawn from the lower left end of the radiator 114. The outlet 124b (see FIG. 3) of each radiator pipe 122 drawn from a position slightly on the left side of the lower surface of the radiator 114 is connected to the front upper part of the water tank 132, and the pipe P14 is an upper rear part of the water tank 132. It is formed in a U shape so that it rises once and then descends. Exhaust gas containing water (water and water vapor) and carbon dioxide discharged from the cathode outlet I4 of the cell stack 102 is given to the radiator 114 via the pipe P12, and the water vapor is liquefied. Exhaust gas from the radiator 114 is supplied to the water tank 132 together with water through the pipe P13, and is discharged to the outside through the pipe P14.

  The pipes P8 to P14 described above mainly serve as an exhaust passage.

  Further, the water tank 132 and the water pump 160 are communicated by a pipe P15, and the water pump 160 and the aqueous solution tank 130 are communicated by a pipe P16. The pipe P15 connects the lower right side of the water tank 132 and the central part of the water pump 160, and the pipe P16 connects the central part of the water pump 160 and the upper left corner of the aqueous solution tank 130. By driving the water pump 160, the water in the water tank 132 is returned to the aqueous solution tank 130 via the pipes P15 and P16.

  The pipes P15 and P16 described above serve as a water flow path.

  The aqueous solution tank 130 and the catch tank 140 are communicated by a pipe P20, the catch tank 140 and the aqueous solution tank 130 are communicated by a pipe P21, and the catch tank 140 and the air chamber 150 are communicated by a pipe P22. The pipe P20 connects the upper left corner of the aqueous solution tank 130 and the upper left corner of the catch tank 140, and the pipe P21 connects the lower end of the catch tank 140 and the lower left corner of the aqueous solution tank 130. The pipe P22 connects a position near the upper left side of the catch tank 140 and the upper end surface of the air chamber 150. The gas (mainly carbon dioxide, vaporized methanol and water vapor) in the aqueous solution tank 130 is given to the catch tank 140 via the pipe P20. The vaporized methanol and water vapor are cooled and liquefied in the catch tank 140, and then returned to the aqueous solution tank 130 through the pipe P21. The gas (carbon dioxide, unliquefied methanol and water vapor) in the catch tank 140 is supplied to the air chamber 150 via the pipe P22.

  The pipes P20 to P22 described above mainly serve as fuel processing channels.

  As shown in FIG. 10, concentration information corresponding to the concentration of the aqueous methanol solution supplied to the cell stack 102 is detected in the vicinity of the anode inlet I1 of the cell stack 102 using the electrochemical characteristics of the aqueous methanol solution. A voltage sensor 168 for detecting the temperature and a temperature sensor 170 for detecting the temperature of the aqueous methanol solution supplied to the cell stack 102 are provided. In this embodiment, the temperature detected by the temperature sensor 170 is regarded as the temperature of the fuel cell 104. The temperature sensor only needs to be installed at any location where the temperature that can be regarded as the temperature of the fuel cell 104 can be detected. For example, the temperature sensor may be provided at the anode outlet I2, the cathode outlet I4, the fuel cell 104, or the like. Further, an outside air temperature sensor 171 for detecting the outside air temperature is provided in the vicinity of the air filter 142. The voltage sensor 168 detects an open circuit voltage of the fuel cell (fuel cell) 104 and uses the voltage value as electrochemical concentration information.

The electrical configuration of such a fuel cell system 100 will be described with reference to FIG.
The controller 156 of the fuel cell system 100 performs necessary calculations to control the operation of the fuel cell system 100, a clock circuit 174 for supplying a clock to the CPU 172, a program and data for controlling the operation of the fuel cell system 100 In addition, a memory 176 made of, for example, an EEPROM for storing calculation data, a reset IC 178 for preventing malfunction of the fuel cell system 100, an interface circuit 180 for connecting to an external device, and an electric motor 60 for driving the motorcycle 10 The voltage detection circuit 184 for detecting the voltage in the electric circuit 182 for connecting the cell stack 102 to the battery cell 102, the current detection circuit 186 for detecting the current flowing through the fuel cell 104 and the cell stack 102, and the electric circuit 182 are opened. An ON / OFF circuit 188 for preventing the overvoltage, a voltage protection circuit 190 for preventing an overvoltage of the electric circuit 182, a diode 192 provided in the electric circuit 182, and a power supply circuit 194 for supplying a predetermined voltage to the electric circuit 182. Including.

  The CPU 172 of the controller 156 receives the detection signals from the voltage sensor 168, the temperature sensor 170, and the outside air temperature sensor 171, the voltage detection value from the voltage detection circuit 184, and the current detection value from the current detection circuit 186. The The CPU 172 also has a detection signal from the fall switch 196 that detects the presence or absence of a fall, an input signal from the main switch 152 for turning on and off the power, and a signal from the input unit 30c for various settings and information input. Is given. Further, the CPU 172 is also provided with detection signals from the level sensors 129, 131 and 133.

  In the memory 176 serving as a storage means, in addition to a program and calculation data for executing the operations shown in FIGS. 15 to 18, electrochemical concentration information (the fuel cell 104) of the aqueous methanol solution obtained by the voltage sensor 168. The conversion information for converting the open circuit voltage) into the concentration is stored. This conversion information is, for example, table data indicating the correspondence between the output information of the voltage sensor and the corresponding density.

  Further, the memory 176 stores table data indicating the relationship between the fuel cell initial temperature and the methanol fuel input amount as shown in FIG. Further, the memory 176 stores a predetermined value (45 ° C. in this embodiment) that is a threshold value to be compared with the fuel cell temperature.

  The CPU 172 controls auxiliary equipment such as the fuel pump 136, the aqueous solution pump 146, the air pump 148, the water pump 160, the cooling fans 120 and 126, the detection valve 138, and the rust prevention valve 158. Further, the CPU 172 controls the display unit 30b for displaying various information and notifying various information to the rider of the motorcycle.

  Further, a secondary battery 134 and a drive unit 62 are connected to the cell stack 102. The secondary battery 134 and the drive unit 62 are connected to the electric motor 60. The secondary battery 134 complements the output from the cell stack 102, is charged by the electric energy from the cell stack 102, and gives electric energy to the electric motor 60 and the auxiliary devices by the discharge.

  A meter 30 a for measuring various data of the electric motor 60 is connected to the electric motor 60, and the data measured by the meter 30 a and the state of the electric motor 60 are given to the CPU 172 via the interface circuit 198.

  The interface circuit 198 can be connected to a charger 200, and the charger 200 can be connected to an external power source (commercial power source) 202. When the charger 200 is connected, a charger connection signal is given to the CPU 172 via the interface circuit 198. The switch 200a of the charger 200 can be turned on / off by the CPU 172.

What should be noted in such a fuel cell system 100 is an aqueous solution tank 130.
Referring to FIG. 12, a holding unit 204 is provided in the aqueous solution tank 130. The holding unit 204 is supported by a support unit 206 attached to the inner surface of the aqueous solution tank 130. The holding unit 204 holds the fuel intake / release member 208.

  Referring to FIG. 13, the fuel intake / release member 208 is made of a host compound, and the fuel intake / release member 208 takes in and immobilizes liquid methanol 210, which is a liquid fuel serving as a guest compound. The inclusion compound 212 is constituted by the fuel intake / release member 208 and the liquid methanol 210.

  By the inclusion compounding technology, the fuel intake / release member 208 as the host compound takes in the liquid methanol 210 contained in the methanol aqueous solution when coming into contact with the methanol aqueous solution having a concentration higher than the predetermined value, and has a concentration lower than the predetermined value. Liquid methanol 210 is released when it comes into contact with an aqueous methanol solution (including water having a zero concentration). In this embodiment, an inclusion compound whose threshold value is 5% is used, but the present invention is not limited to this. Thus, the host compound after releasing the liquid methanol 210 from the inclusion compound 212 has a selective inclusion ability with respect to the liquid methanol 210 and can be effectively reused for inclusion of the liquid methanol 210.

  The holding unit 204 may hold the fuel intake / release member 208 but does not hold the methanol aqueous solution (the methanol aqueous solution slips through). The shape of the fuel intake / release member 208 may be powdery or granular.

  In addition, as shown in FIG. 12, the liquid level in the aqueous solution tank 130 can be held within the range A based on the output from the level sensor 131. The lowest height X1 in the range of A is desirably a position where the host compound 208 and thus the clathrate compound are immersed in the methanol aqueous solution.

  In this embodiment, the aqueous solution tank 130 corresponds to the first aqueous solution holding unit. The CPU 172 corresponds to the operation control unit. The water tank 132 corresponds to water holding means. The fuel supply means includes a fuel tank 128, pipes P1 and P2, and a fuel pump 136. The water supply means includes a water tank 132, pipes P15 and P16, and a water pump 160. The water supply means includes pipes P15 and P16 and a water pump 160.

Next, main operations during operation of the fuel cell system 100 will be described.
After the main switch 152 is turned on, the fuel cell system 100 drives auxiliary equipment such as the aqueous solution pump 146 and the air pump 148 and starts operation.

  By driving the aqueous solution pump 146, the aqueous methanol solution stored in the aqueous solution tank 130 is sent from the pipe P 3 side to the pipe P 4 side and supplied to the aqueous solution filter 144. The methanol aqueous solution from which impurities and the like have been removed by the aqueous solution filter 144 is directly supplied to the anode 104b of each fuel cell 104 constituting the cell stack 102 via the pipe P5 and the anode inlet I1.

  On the other hand, the air (air) drawn from the air filter 142 by driving the air pump 148 is silenced by flowing into the air chamber 150 via the pipe P8. Then, the sucked air and the gas from the catch tank 140 given to the air chamber 150 are supplied to the cathode 104c of each fuel cell 104 constituting the cell stack 102 via the pipes P9 to P11 and the cathode inlet I3. The

  In the anode 104b of each fuel cell 104, methanol and water in the supplied aqueous methanol solution chemically react to generate carbon dioxide and hydrogen ions. The generated hydrogen ions flow into the cathode 104c through the electrolyte membrane 104a, and electrochemically react with oxygen in the air supplied to the cathode 104c side to generate water (water vapor) and electric energy. That is, power generation is performed in the cell stack 102. The generated electric energy is sent to and stored in the secondary battery 134 and is used for driving the motorcycle 10 and the like.

  On the other hand, the carbon dioxide and unreacted methanol aqueous solution generated at the anode 104b of each fuel cell 104 rise in temperature due to the heat generated by the electrochemical reaction (for example, about 65 ° C. to 70 ° C.), and unreacted methanol. A part of the aqueous solution is vaporized. The carbon dioxide and the unreacted aqueous methanol solution flow into the aqueous solution radiator 112 via the anode outlet I2 of the cell stack 102, and are cooled by the fan 120 while flowing through the radiator pipe 116 (for example, about 40 ° C.). . The cooled carbon dioxide and the unreacted methanol aqueous solution are returned to the aqueous solution tank 130 via the pipe P7.

  On the other hand, most of the water vapor generated at the cathode 104c of each fuel cell 104 is liquefied and converted into water and discharged from the cathode outlet I4 of the cell stack 102, but the saturated water vapor is discharged in a gas state. A part of the water vapor discharged from the cathode outlet I4 is cooled by the radiator 114 and liquefied by lowering the dew point. The water vapor liquefaction operation by the radiator 114 is performed by operating the fan 126. Water (water and water vapor) from the cathode outlet I4 is supplied to the water tank 132 through the pipe P12, the radiator 114 and the pipe P13 together with unreacted air.

  Further, in the cathode 104c of each fuel cell 104, the vaporized methanol from the catch tank 140 and the methanol moved to the cathode by the crossover react with oxygen in the platinum catalyst layer and decompose into harmless moisture and carbon dioxide. . Moisture and carbon dioxide decomposed from methanol are discharged from the cathode outlet I4 and supplied to the water tank 132 via the radiator 114. Further, the water moved to the cathode 104c of each fuel cell 104 due to the water crossover is discharged from the cathode outlet I4 and supplied to the water tank 132 via the radiator 114.

  The water collected in the water tank 132 is appropriately refluxed to the aqueous solution tank 130 through the pipes P15 and P16 by driving the water pump 160, and used as water of the methanol aqueous solution.

  In the fuel cell system 100 in operation, the concentration detection process of the aqueous methanol solution is periodically executed in order to cause each fuel cell 104 to efficiently generate power while preventing the deterioration of each fuel cell 104. Based on the detection result, the methanol concentration of the aqueous methanol solution in the aqueous solution tank 130 to be supplied to the cell stack 102 is adjusted to about 3 wt%, for example. Specifically, the fuel pump 136 and the water pump 160 are controlled by the controller 156, and based on the detection result of the methanol concentration, the methanol fuel in the fuel tank 128 is supplied to the aqueous solution tank 130, and the water in the water tank 132 is changed. The solution is returned to the aqueous solution tank 130.

  With reference to FIG. 15 and FIG. 16, the operation related to the adjustment of the fuel concentration of the fuel cell system 100 will be described. Initially, the fuel intake / release member 208 and the methanol aqueous solution are isolated.

  The flow charts shown in FIGS. 15 and 16 include the fuel intake process (1) (steps S3 to S9) and the fuel intake process (2) (steps S35 to S39). Either one is executed. do it. Here, a mode for executing the fuel intake process (1) will be described.

  First, the CPU 172 confirms whether the main switch 152 is turned on and a fuel cell activation signal is input (step S1). The system waits until the fuel cell activation signal is input. When the fuel cell activation signal is input, the fuel input amount stored in the memory 176 is called (step S3). Then, the fuel pump 136 is driven (step S5), and high-concentration methanol fuel corresponding to the stored input amount is input (step S7). If there is no fuel input data, the default value is used. Thereby, the liquid methanol 210 is taken in and held in the fuel take-in / release member 208 (step S9). Then, the water pump 160 or the fuel pump 136 and the water pump 160 are driven, and the liquid level in the aqueous solution tank 130 is adjusted to fall within the range A shown in FIG. 12 (step S11).

  Thereafter, the aqueous solution pump 146, the air pump 148, etc. are driven to start power generation (step S13). At this time, the adjustment of the liquid level in the aqueous solution tank 130 is continued. Then, the concentration of the aqueous methanol solution in the aqueous solution tank 130 is automatically adjusted to the first concentration by performing the intake / release of the liquid methanol 210 by the fuel intake / release member 208 (step S15). The temperature of the fuel cell 104 is detected (step S17), and it is determined whether the temperature is 45 ° C. or higher (step S19). The concentration adjustment by the fuel intake / release member 208 is continued until the fuel cell temperature reaches 45 ° C. or higher. During this time, fuel is not replenished. Therefore, a sufficient amount of fuel is kept in the aqueous solution tank 130 until the fuel cell temperature reaches 45 ° C. until the start of power generation in step S13. However, refueling after the start of power generation is not prohibited. Further, the first concentration and the concentration during normal operation (second concentration) may be substantially the same, but in order to shorten the temperature rising time at the start, the first concentration is set to be higher than the concentration during normal operation. It is desirable to increase it, and in this embodiment it is set to 5%.

  When the fuel cell temperature becomes 45 ° C. or higher in step S19, the concentration information of the methanol aqueous solution is obtained by the voltage sensor 168 which is an electrochemical sensor, and the concentration information is converted into the concentration by the CPU 172 based on the conversion information in the memory 176. Thus, the methanol concentration is obtained (step S21). The CPU 172 controls the operation of the fuel pump 136 and the water pump 160 based on the detected concentration, whereby the concentration of the methanol aqueous solution is controlled to the second concentration (step S23), and whether the fuel cell stop signal is input or not is determined by the CPU 172. (Step S25). Concentration control based on the voltage sensor 168 is continued until the fuel cell stop signal is input. In this embodiment, the second concentration is set to 3%, for example. Thus, by making the second concentration lower than the first concentration, it is possible to maintain a state in which the liquid methanol 210 as the fuel is not held in the fuel intake / release member 208.

  When the fuel cell stop signal is input in step S25, the concentration of the aqueous solution is detected using the voltage sensor 168 (step S27) so that the liquid methanol 210 that can be held in the fuel intake / release member 208 can be supplied. The fuel input amount is calculated (step S29), and the calculated fuel input amount is stored in the memory 176 (step S31).

  Here, if the concentration of the aqueous methanol solution in the aqueous solution tank 130 is lower than the first concentration, the amount of liquid methanol 210 to be supplied can be calculated.

  For example, the fuel intake / release member 208 adjusts the aqueous methanol solution in the aqueous solution tank 130 to 5%. The amount of liquid methanol 210 that can be held in the fuel intake / release member 208 is 200 ml, and the fuel intake / release is If the volume of the member 208 is 300 ml and the methanol aqueous solution remaining in the holding unit 204 after the liquid level lowering described later (here, the holding unit 204 can also hold the aqueous solution) is 50 ml, the concentration of the methanol aqueous solution at that time will be Accordingly, the following amount of liquid methanol 210 is supplied.

  When the concentration of the methanol aqueous solution is 3%, 2%, and 1%, the fuel intake / release member 208 does not hold the liquid methanol 210, and therefore 200 ml of the liquid methanol 210 can be taken in. Further, in order to make the methanol aqueous solution remaining in the holding unit 204 5%, approximately 1 ml, 1.5 ml, and 2 ml of liquid methanol 210 are required, respectively. Accordingly, the amounts of liquid methanol 210 to be supplied are approximately 201 ml, 201.5 ml, and 202 ml, respectively. Based on this, the amount of methanol fuel input is determined. Note that the amount of methanol fuel input may be determined so that the amount of liquid methanol 210 supplied is 200 ml regardless of the concentration.

  Then, the liquid level in the aqueous solution tank 130 is lowered to, for example, the height X2 (see FIG. 12) so that the fuel intake / release member 208 and the aqueous methanol solution do not come into contact with each other (step S33), and the fuel intake process (2) The power generation stop process is performed without performing (Steps S35 to S39) (Step S41), and the process ends. The operation of lowering the liquid level is performed by continuing power generation in a state where the replenishment amount of methanol fuel and water is reduced.

  According to such a fuel cell system 100, the fuel intake / release member 208 is inserted into the aqueous methanol solution held in the aqueous solution tank 130 by using the inclusion compounding technique, and the fuel intake / release member 208 and the aqueous methanol solution are combined. By contacting, the concentration of the methanol aqueous solution can be made constant. In the fuel cell system 100 of the type that circulates and uses the aqueous methanol solution, the concentration of the aqueous methanol solution is controlled without performing concentration control by inserting the fuel intake / release member 208 into the aqueous solution tank 130 whenever the concentration control is required. Can be stabilized. Further, the concentration can be changed by removing the fuel intake / release member 208 from the aqueous methanol solution. This is particularly effective at startup.

  Further, by controlling the amount of methanol fuel and water supplied to the aqueous solution tank 130, the amount of the methanol aqueous solution in the aqueous solution tank 130 can be easily adjusted, and the fuel can be taken into the aqueous methanol solution held in the aqueous solution tank 130. -The entrance / exit of the discharge member 208 can be easily controlled.

  Further, by disposing the fuel intake / release member 208 in the holding unit 204, a high concentration aqueous methanol solution can be easily supplied to the fuel intake / release member 208. The liquid methanol 210 can be quickly held.

  Further, by holding the liquid methanol 210 in the fuel intake / release member 208 immediately before supplying the liquid methanol 210 to the fuel cell 104, the liquid methanol 210 is not vaporized and evaporated, and the fuel efficiency can be improved.

Next, a mode for executing the fuel intake process (2) will be described.
In this mode, if the liquid methanol 210 is not initially held on the fuel intake / release member 208, a predetermined amount of the liquid methanol 210 is supplied and held.

  15 and 16, when the fuel cell activation signal is input in step S1, the process proceeds to step S11 without executing the fuel intake process (1) (steps S3 to S9), and the methanol aqueous solution The liquid level is adjusted. Thereafter, steps S13 to S33 are executed in the same manner as described above. After the liquid level in the aqueous solution tank 130 is lowered so that the fuel intake / release member 208 and the aqueous methanol solution do not contact each other in step S33, the fuel pump 136 is driven (step S35) and stored in step S31. A high-concentration methanol fuel corresponding to the input amount is input (step S37). Thereby, the liquid methanol 210 is taken in and held in the fuel take-in / release member 208 (step S39). Then, a power generation stop process is performed (step S41), and the process ends.

  According to this mode, the next start-up of the fuel cell 104 can be smoothly performed by holding the liquid methanol 210 in the fuel intake / release member 208 after the stop instruction of the fuel cell 104.

  In the operations shown in FIGS. 15 and 16, the second concentration may be higher than the first concentration. In this case, since the liquid methanol 210 is always filled in the fuel intake / release member 208, the liquid methanol 210 is supplied to the fuel intake / release member 208 after the stop instruction of the fuel cell 104 or immediately after the next start-up. There is no need to supply.

  Next, another operation mode of the fuel cell system 100 will be described with reference to FIGS. 17 and 18. Initially, the fuel intake / release member 208 and the methanol aqueous solution are isolated. In addition, it is a precondition that the operation mode is started in a state where the liquid methanol 210 is not taken into the fuel take-in / release member 208.

  In this mode, when a fuel cell activation signal is input in step S1, the temperature of the fuel cell 104 is detected by the temperature sensor 170 (step S2a), and it is determined whether the temperature is 45 ° C. or higher (step S2b). ). If the fuel cell temperature is lower than 45 ° C., the fuel input amount is calculated according to the fuel cell temperature with reference to the table data corresponding to FIG. 14 stored in the memory 176 (step S2c), and the fuel pump 136 is driven. (Step S5), high-concentration methanol fuel corresponding to the calculated input amount is input (Step S7). Thereafter, the processes of steps S9 to S25 are executed in the same manner as described above. On the other hand, in step S2b, if the temperature of the fuel cell 104 is 45 ° C. or higher, the water pump 160 or the fuel pump 136 and the water pump 160 are driven, and the liquid level in the aqueous solution tank 130 is A in FIG. Adjustment is made so as to be within the range (step S11a), and then the aqueous solution pump 146 and the air pump 148 are driven to start power generation (step S13a), and the process proceeds to step S21.

  When the fuel cell stop signal is input in step S25, the liquid level in the aqueous solution tank 130 is adjusted, and the liquid level is lowered so that the fuel intake / release member 208 and the aqueous methanol solution do not contact each other (step S33a). . Then, power generation stop processing is performed (step S41a), and the process ends.

  According to this mode, the amount of methanol fuel input can be appropriately determined according to the temperature of the fuel cell at the time of startup.

  In this mode, the following operation may be performed. When power generation of the fuel cell 104 is stopped before the fuel cell temperature reaches 45 ° C. in step S19, the fuel cell temperature at that time is stored, and the temperature stored in step S2c at the next start-up is stored. After subtracting the input amount (see FIG. 14), methanol fuel is input.

  Further, in the fuel cell system 100, as shown in FIGS. 10 and 11, an aqueous solution tank 130a for allowing the methanol aqueous solution to be withdrawn or returned is separately provided, and the operation of the aqueous solution pumps 146a and 146b is controlled by the CPU 172. The methanol aqueous solution may be evacuated or returned. In this case, the amount of liquid in the aqueous solution tank 130 can be quickly changed, and the fuel intake / release member 208 can be quickly controlled in and out of the aqueous methanol solution held in the aqueous solution tank 130. In this embodiment, the aqueous solution tank 130a corresponds to the second aqueous solution holding unit. The first supply means includes an aqueous solution pump 146a, and the second supply means includes an aqueous solution pump 146b. If a pump capable of reverse rotation is used as the aqueous solution pump, one pump is sufficient. Moreover, you may make it perform any one of evacuation and return of methanol aqueous solution by gravity or capillary action. In this case, either one of the aqueous solution pumps 146a and 146b is not necessary and can be replaced with a valve mechanism that controls opening and closing by the CPU 172.

  Further, the water tank 132 is also used as the aqueous solution tank 130a, the water pump 160 is also used as the aqueous solution pump 146a, the operation of the water pump 160 is controlled by the CPU 172, and fuel is taken into the aqueous methanol solution held in the aqueous solution tank 130. The entrance / exit of the discharge member 208 may be controlled.

  Further, the water tank 132 is also used as the aqueous solution tank 130a, the water pump 160 is also used as the aqueous solution pump 146b, and the aqueous solution tank 130 and the water tank 132 are connected via a valve 161 (see FIGS. 10 and 11). The operations of the water pump 160 and the valve 161 may be controlled to control the fuel intake / release member 208 to and from the methanol aqueous solution held in the aqueous solution tank 130. In this embodiment, the first supply means includes a valve 161.

  In these cases, the amount of liquid in the aqueous solution tank 130 can be changed with a simple configuration without separately providing the aqueous solution tank 130a.

  The mode of changing the liquid level of the aqueous methanol solution in the aqueous solution tank 130 is not limited to the above-described mode, and the level of the aqueous methanol solution in the aqueous solution tank 130 is changed by an arbitrary method. The contact with the methanol aqueous solution can be controlled.

  Further, as shown in FIG. 19, a hoisting machine 214 may be provided on the upper surface of the aqueous solution tank 130, and the holding unit 204 may be connected to the wire 216 of the hoisting machine 214 so that the holding unit 204 can be moved in the vertical direction. . In this case, the hoisting machine 214 corresponds to the support part.

  Also in this case, the operations shown in FIGS. 15 and 16 and the operations shown in FIGS. 17 and 18 can be executed. However, the liquid level adjustment process of steps S11 and S11a is replaced with the process of lowering the fuel intake / release member 208 and putting it into the methanol aqueous solution, and the liquid level adjustment process of steps S33 and S33a is the fuel intake / release member 208. It is desirable to change to a process of raising the pH and taking out from the aqueous methanol solution.

  In this embodiment, by controlling the operation of the hoisting machine 214 by the CPU 172, the vertical position of the holding unit 204 and thus the fuel intake / release member 208 can be changed, and the aqueous methanol solution held in the aqueous solution tank 130 can be changed. The fuel take-in / release member 208 can be easily taken in and out. Further, by moving the fuel intake / release member 208 to the vicinity of the aqueous solution outlet of the aqueous solution tank 130, a methanol aqueous solution close to the target concentration can be reliably supplied to the anode 104b of the fuel cell 104.

  Further, a rail extending in the vertical direction is formed on the inner surface of the aqueous solution tank 130, and the holding portion 204, and thus the fuel intake / release member 208 is moved in the vertical direction by sliding the holding portion 204 on the rail. Also good.

  The present invention is suitably used for a motorcycle 10 including the fuel cell system 100, and thus, for transportation equipment such as automobiles and ships.

  Note that the conversion information for obtaining the concentration of the methanol aqueous solution may be an arithmetic expression for converting the concentration information into the concentration.

  In the above-described embodiment, the case where the liquid fuel serving as the guest compound is the liquid methanol 210 has been described, but the present invention is not limited to this. Any liquid fuel may be used as long as it can be used as a fuel for the fuel cell 104. Examples thereof include other alcohols, ethers, hydrocarbons, and acetals. Specifically, the liquid fuel includes alcohols such as methanol, ethanol, n-propanol, isopropanol and ethylene glycol, ethers such as dimethyl ether, methyl ethyl ether and diethyl ether, hydrocarbons such as propane and butane, and dimethoxymethane. And acetals such as trimethoxymethane. These may be used alone or in combination of two or more.

  Further, as host compounds, those composed of organic compounds, inorganic compounds and organic / inorganic composite compounds are known, and as organic compounds, monomolecular, polymolecular, and polymeric hosts are known. ing.

  Monomolecular host compounds include cyclodextrins, crown ethers, cryptands, cyclophanes, azacyclophanes, calixarenes, cyclotriveratrylenes, spherands, cyclic oligopeptides, etc. . Examples of the multi-molecular host compound include ureas, thioureas, deoxycholic acids, perhydrotriphenylenes, tri-o-thymotides, beansryls, spirobifluorenes, cyclophosphazenes, monoalcohols, Diols, acetylene alcohols, hydroxybenzophenones, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, bixanthenes, Examples thereof include carboxylic acids, imidazoles, and hydroquinones. In addition, examples of the polymer host compound include celluloses, starches, chitins, chitosans, polyvinyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2-tetrakisphenylethane as a core, α, Examples include polyethylene glycol arm type polymers having α, α ′, α′-tetrakisphenylxylene as a core.

  In addition, an organophosphorus compound, an organosilicon compound, etc. are also mentioned.

  Examples of inorganic host compounds include titanium oxide, graphite, alumina, transition metal dicargogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, and porous glass. It is done.

  In addition, some organometallic compounds exhibit properties as host compounds, such as organoaluminum compounds, organotitanium compounds, organoboron compounds, organozinc compounds, organoindium compounds, organogallium compounds, organotellurium compounds, organotin compounds. , Organic zirconium compounds, and organic magnesium compounds. Moreover, it is also possible to use a metal salt of an organic carboxylic acid, an organic metal complex, or the like, but it is not particularly limited as long as it is an organic metal compound.

  Of these host compounds, multi-molecular host compounds whose inclusion ability is hardly influenced by the molecular size of the guest compound are preferable.

  Specific examples of the multimolecular host compound include urea, 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol, and 1,1-bis (2,4-dimethyl). Phenyl) -2-propyn-1-ol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1,6,6-tetrakis (2,4-dimethylphenyl)- 2,4-hexadiyne-1,6-diol, 9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis (4-methylphenyl) -9,10-dihydroanthracene- 9,10-diol, 1,1,2,2-tetraphenylethane-1,2-diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 2, 2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonylbisphenol, 2,2'-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-ethylidenebisphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy) -5-t-butylphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethylene, 1,1,2, 2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) Ethane, α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene, tetrakis (p-methoxyphenyl) ethylene, 3,6,3 ′, 6′-tetramethoxy-9,9 ′ -Bi-9H-xanthene, 3,6,3 ', 6'-tetraacetoxy-9,9'-bi-9H-xanthene, 3,6,3', 6'-tetrahydroxy-9,9'-bi -9H-xanthene, gallic acid, methyl gallate, catechin, bis-β-naphthol, α, α, α ′, α′-tetraphenyl-1,1′-biphenyl-2,2′-dimethanol, diphenic acid Bisdicyclohexylamide, bisdicyclohexylamide fumarate, cholic acid, deoxycholic acid, 1,1,2,2-tetraphenylethane, tetrakis (p-iodophenyl) ethylene, 9,9′-bianthryl, 1,1,2 , 2- Tetrakis (4-carboxyphenyl) ethane, 1,1,2,2-tetrakis (3-carboxyphenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenylimidazole, 1,2,4,5-tetraphenyl Imidazole, 2-phenylphenanthro [9,10-d] imidazole, 2- (o-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (m-cyanophenyl) phenanthro [9,10-d ] Imidazole, 2- (p-cyanophenyl) phenanthro [9,10-d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4 -Dimethylphenyl) hydroquinone, and the like.

  Among the compounds described above, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4 -Hydroxyphenyl) phenolic host compounds such as ethylene, diphenic acid bis (dicyclohexylamide), amide based host compounds such as fumaric acid bisdicyclohexylamide, 2- (m-cyanophenyl) phenanthro [9,10-d] An imidazole host compound such as imidazole is advantageous in terms of inclusion ability, and in particular, a phenol host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane is advantageous in terms of easy industrial use. It is.

  These host compounds may be used individually by 1 type, and may use 2 or more types together.

  These host compounds may be compounds of any shape as long as they can form a solid clathrate compound.

  Of the above host compounds, organic host compounds can also be used as an organic / inorganic composite material supported on a porous material. In this case, examples of the porous material supporting the organic host compound include intercalation compounds such as clay minerals and montmorillonites in addition to silicas, zeolites and activated carbons, but are not limited thereto. is not. Such an organic / inorganic composite material is prepared by dissolving the above-mentioned organic host compound in a solvent capable of dissolving it, impregnating the solution in a porous material, drying the solvent, drying under reduced pressure, etc. It can be manufactured by the method. The amount of the organic host compound supported on the porous material is not particularly limited, but is usually about 10 to 80% by weight based on the porous material.

  Examples of the method for synthesizing an inclusion compound using a host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane described above include a method in which a fuel and a host compound are directly contacted and mixed. It is possible to easily synthesize an inclusion compound containing liquid fuel.

  In the synthesis of the clathrate compound, the temperature at which the fuel and the host compound are brought into contact with each other is not particularly limited, but is preferably from room temperature to about 100 ° C. There is no particular limitation on the pressure condition at this time, but it is preferably performed in a normal pressure environment. The time for contacting the fuel and the host compound is not particularly limited, but is preferably about 0.01 to 24 hours from the viewpoint of work efficiency.

  The clathrate compound thus obtained varies depending on the type of the host compound used, the contact condition with the fuel, etc., but usually the clathrate in which 0.1 to 10 moles of fuel molecules are clathrated per mole of the host compound. It is a contact compound.

1 is a left side view showing a motorcycle according to an embodiment of the present invention. It is the perspective view which looked at the arrangement state of the fuel cell system with respect to the body frame of a motorcycle from the diagonally left front. It is the perspective view which looked at the arrangement state of the fuel cell system with respect to the body frame of a motorcycle from diagonally left rear. It is a left view which shows the piping state of a fuel cell system. It is a right view which shows the piping state of a fuel cell system. It is the perspective view which looked at the piping state of the fuel cell system from diagonally left forward. It is the perspective view which looked at the piping state of the fuel cell system from diagonally right forward. It is an illustration figure which shows a fuel cell stack. It is an illustration figure which shows a fuel cell. It is a system diagram which shows piping of a fuel cell system. It is a block diagram which shows the electric constitution of a fuel cell system. It is an illustration figure which shows the structure in an aqueous solution tank. It is an illustration figure for demonstrating an inclusion compound. It is a graph which shows the amount of methanol fuel (high concentration methanol aqueous solution) input with respect to fuel cell initial temperature. It is a flowchart which shows an example of operation | movement of this invention. FIG. 16 is a flowchart showing a continuation of the operation shown in FIG. 15. It is a flowchart which shows the other example of operation | movement of this invention. FIG. 18 is a flowchart showing a continuation of the operation shown in FIG. 17. It is an illustration figure which shows the other example of a support part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Motorcycle 100 Fuel cell system 102 Fuel cell stack 104 Fuel cell (fuel cell)
128 Fuel tank 130, 130a Aqueous solution tank 132 Water tank 136 Fuel pump 146, 146a, 146b Aqueous solution pump 156 Controller 160 Water pump 161 Valve 168 Voltage sensor 170 Temperature sensor 172 CPU
176 Memory 204 Holding portion 206 Support portion 208 Fuel intake / release member 210 Liquid methanol 212 Inclusion compound 214 Winding machine P1 to P16, P20 to P22 Pipe

Claims (14)

A fuel cell system that circulates and uses an aqueous fuel solution,
A fuel cell that generates electrical energy through an electrochemical reaction;
First aqueous solution holding means for holding the aqueous fuel solution supplied to the fuel cell;
A fuel intake comprising a host compound that takes in the liquid fuel contained in the aqueous fuel solution when coming into contact with the aqueous fuel solution having a concentration higher than a predetermined value and releases the liquid fuel when brought into contact with the aqueous fuel solution having a concentration lower than the predetermined value. A fuel cell system, comprising: a charging / discharging member; and a control unit that controls the fuel intake / release member to and from the fuel aqueous solution held by the first aqueous solution holding unit. The control means includes
Fuel replenishing means for replenishing the first aqueous solution holding means with fuel having a concentration equal to or higher than the aqueous fuel solution;
Water replenishing means for replenishing water to the first aqueous solution holding means, and the fuel replenishing means for controlling the fuel intake / release member to and from the fuel aqueous solution held by the first aqueous solution holding means; The fuel cell system according to claim 1, further comprising an operation control unit that controls an operation of the water supply means. The control means includes
Second aqueous solution holding means for holding the aqueous fuel solution;
First supply means for supplying the aqueous fuel solution from the first aqueous solution holding means to the second aqueous solution holding means;
Second supply means for supplying the aqueous fuel solution from the second aqueous solution holding means to the first aqueous solution holding means, and the fuel intake / release member in and out of the aqueous fuel solution held by the first aqueous solution holding means 2. The fuel cell system according to claim 1, further comprising an operation control unit configured to control operations of the first supply unit and the second supply unit in order to control the operation. Water holding means for holding water discharged from the fuel cell, and water supply means for supplying water held in the water holding means to the first aqueous solution holding means,
The water holding means also serves as the second aqueous solution holding means, the water supply means serves as the first supply means or the second supply means,
The said operation control part controls operation | movement of the said water supply means in order to control the entrance / exit of the said fuel intake / release member to the said aqueous fuel solution hold | maintained at the said 1st aqueous solution holding means. Fuel cell system. The control means includes
A holding portion for holding the fuel intake / release member;
A support unit for movably supporting the holding unit; and controlling the operation of the support unit to control the fuel intake / release member to and from the fuel aqueous solution held by the first aqueous solution holding unit. The fuel cell system according to claim 1, comprising an operation control unit. A fuel replenishing means for replenishing the first aqueous solution holding means with a fuel having a concentration equal to or higher than the aqueous fuel solution; and a fuel supply / release member which is disposed in the first aqueous solution holding means and supplied with the fuel. The fuel cell system according to claim 1, further comprising a holding portion.   Transportation equipment comprising the fuel cell system according to claim 1. An operation method of a fuel cell system that circulates and uses an aqueous fuel solution,
The fuel aqueous solution supplied to the fuel cell is held by the first aqueous solution holding means, and when it comes into contact with the fuel aqueous solution having a concentration higher than a predetermined value, the liquid fuel contained in the fuel aqueous solution is taken in and the concentration is lower than the predetermined value. A fuel intake / release member made of a host compound that releases liquid fuel when contacted with the aqueous fuel solution is disposed in the first aqueous solution holding means, and the fuel intake / release member and the aqueous fuel solution are brought into contact with each other. The operation method of the fuel cell system, wherein the concentration of the aqueous fuel solution present in the first aqueous solution holding means is adjusted accordingly.   9. The operating method of a fuel cell system according to claim 8, wherein contact between the fuel intake / release member and the aqueous fuel solution is controlled by changing a liquid level of the aqueous fuel solution in the first aqueous solution holding means.   The first aqueous solution holding means is present in the first aqueous solution holding means by controlling the replenishment amount of water supplied to the first aqueous solution holding means and the replenishment amount of the fuel having a concentration equal to or higher than the aqueous fuel solution to the first aqueous solution holding means. The operation method of the fuel cell system according to claim 8, wherein the amount of the aqueous fuel solution is adjusted to control contact between the fuel intake / release member and the aqueous fuel solution.   By controlling the supply amount of the aqueous fuel solution from the first aqueous solution holding means to the second aqueous solution holding means and the supply amount of the aqueous fuel solution from the second aqueous solution holding means to the first aqueous solution holding means, 9. The method of operating a fuel cell system according to claim 8, wherein the amount of the aqueous fuel solution present in the aqueous solution holding means is adjusted to control contact between the fuel intake / release member and the aqueous fuel solution.   The fuel intake / release member is movably held, and the fuel intake / release member is moved to control contact between the fuel intake / release member and the aqueous fuel solution in the first aqueous solution holding means. The operation method of the fuel cell system according to claim 8.   The operation method of the fuel cell system according to claim 8, wherein after the start instruction of the fuel cell, liquid fuel is held in the fuel intake / release member. 9. The method of operating a fuel cell system according to claim 8, wherein after the fuel cell stop instruction, the fuel intake / release member holds liquid fuel.

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