Abstract:
Problem: The fuel supply means for small fuel cells, including portable ones, must be of a small size that permits portable applications, be lightweight and be given a constant chemical reaction rate when fuel gas is continuously generated and supplied in a constant amount by a chemical reaction means. Solution: The problem described above was solved by making the chemical reaction concentration in the chemical reaction space universal over time by supplying the chemical reaction solution supplied at a constant rate and providing a first chemical reaction space where there is minimization for that reaction rate and a second chemical reaction space linked thereto. Furthermore, for simplification and size reduction, the second chemical reaction space is housed in a space linked to a solution storage space for at least one of the first and second above.

Description:
FIELD OF THE INVENTION  
       [0001]     The present invention relates to a gas generation and supply device for small fuel cells that makes the chemical reaction rate constant and continuously supplies a constant amount of fuel gas.  
       BACKGROUND OF THE INVENTION  
       [0002]     Various storage and supply methods have been developed and proposed up to this point as fuel supply means for portable or stationary fuel cells. One attempt, a fuel supply means that makes use of a chemical reaction aimed at practical applications has come to be widely proposed as a lightweight, inexpensive method where the amount of fuel storage is greater than other methods. However, there is an urgent need for making the chemical reaction rate constant and making a device that continuously provides a stable supply of fuel gas in a constant quantity with a small inexpensive structure that can be made portable.  
         [0003]     [Patent References 1] Published Unexamined Patent Application No. 2005-19517, Published Unexamined Patent Application No. 200-93104, Published Unexamined Patent Application No. 2004-318683, Published Unexamined Patent Application No. 2000-161509, Patent Application 2005-321503.  
         [0004]     [Non-Patent Reference 1] Nikkei Electronics, Jun. 6, 2005, No. 901 “Borohydride Enters the Fray for Portable Fuel Cells  
       DISCLOSURE OF THE INVENTION  
       [0005]     [Problems to be Solved by the Invention] 
         [0006]     To make the fuel supply stable using a small, simple and inexpensive structure when the fuel cell output is, for example, for applications that are under several lots to applications out of several kilowatts:  
         [0007]     The first problem is the necessity for stabilizing the reaction rate by having a constant concentration for the solution at the site of the chemical reaction without its becoming diluted as the reaction progresses over time.  
         [0008]     The second problem is the problem of achieving an inexpensive, safe supply device with a small, simple structure capable of being used in portable and stationary applications aimed at popularization.  
       SUMMARY OF THE INVENTION  
       [0009]     To solve the problems above, a first aspect of the invention is a gas generation and supply device comprising a first chemical reaction space for continuously generating a constant amount of fuel gas by a chemical reaction through the mixing of a solution supplied by a first constant solution supply means and a particulate material and a second chemical reaction space linked to that first chemical reaction space. To make rate of dilution of the chemical reaction solution concentration with the passage of time slow, the volume of the first chemical reaction space is smaller than that of the solution supply means.  
         [0010]     The second aspect of the invention is the gas generation and supply device wherein a supply outlet for the solution supply means is provided with the particulate material around it in a position separated from a communicating opening and the central part of the first chemical reaction space and is set so that the supply solution does not flow into the communicating opening directly while it is insufficient for the chemical reaction.  
         [0011]     The third aspect of the invention is the gas generation and supply device wherein the particulate material is housed in a material provided with at least a partial opening and formed from at least one other material having solution permeability, the contact with the solution supplied being restricted and there being a structure that prevents early dissolution of the particulate material.  
         [0012]     The fourth aspect of the invention is the gas generation and supply device wherein, even when a second solution that produces the fuel gas by a chemical reaction is used instead of the particulate material, the first chemical reaction space, which is capable of a constant rate chemical reaction, and the second chemical reaction space linked to that space are provided, and the first chemical reaction space is smaller in volume than the solution supply means.  
         [0013]     The fifth aspect of the invention is the gas generation and supply device wherein there is provided a material that adsorbs the solution and maintains the concentration of the solution to keep the solution for the chemical reaction in the first chemical reaction space so that the chemical reaction is insufficient by diffusion in a mobile state, particularly when it is portable.  
         [0014]     The sixth aspect of the invention is the gas generation and supply device wherein there is provided the first reaction space and the second reaction space regardless of whether the chemical reaction for producing the fuel gas is the solution and the particulate material or a mixture of two different solutions. The first chemical reaction space has a space size that corresponds to the chemical reaction rate, and the concentration of the solution supplied at a constant rate by the solution supply means is made constant.  
         [0015]     The seventh aspect of the invention is the gas generation and supply device made simpler and smaller with the second chemical reaction space disposed within a storage body along with the solution supply means.  
       ADVANTAGE OF THE INVENTION  
       [0016]     According to the first through sixth aspects of the invention, it is possible to make the chemical reaction rate constant when portable even in a state of mobile use regardless of the chemical reaction being from the solution and particulate material or from two different solutions, and a continuous supply of a constant amount of fuel gas to the fuel cell is achieved by the same concept. Furthermore, the fuel supply pressure adjustment valve that was necessary when fuel was supplied by a high-pressure tank storing a metal hydride has been made unnecessary by the present invention.  
         [0017]     According to the seventh aspect of the invention, it is possible to use a reduced space for the solution supply by disposing the second chemical reaction space in the storage body along with the solution supply means. There is no need to provide a new space, and compactness and reduced weight may be achieved.  
       DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0018]     In the following, embodiments of the present invention will be described based on the drawings  
         [0019]      FIG. 1  is a block diagram of a hydrogen gas generation and supply device that generates and supplies hydrogen gas by a chemical reaction to supply fuel gas to a small, portable fuel cell, for example, in a first embodiment of the present invention.  
         [0020]     The gas generation and supply device of the present invention comprises three parts, a storage body  3  housing a solution storage body  1  and a first chemical reaction space  30  and a second chemical reaction space  15 . In the solution storage body  1 , for example, a hydrogen resistant fluorine based rubber balloon  14  housing a body (for example, a body partially or completely transparent to a small volume of hydrogen gas at a low pressure of approximately 0.1 Pa or less)  11  and a solution (for example, an aqueous solution of malic acid or hydrochloric acid) adjusted in advance to a prescribed concentration)  10  is linked to a first reaction space  30  through a supply opening  10   a , and the solution  10  may be continuously supplied by a supply opening  10   b  to the reaction space  30  at a constant rate. A second reaction space  15  and the balloon  14  are housed together in a gas permeable material (for example, a carbon cloth, Gortex or the like, prevents liquid from passing through)  13 , and compactness may be enhanced. The outer periphery of the second reaction space  15  is provided with a gas flow space  12  that is linked to a gas outlet  300 .  
         [0021]     The storage body  3  houses a particulate material (for example, specially processed aluminum alloy, borohydride, or the like)  20  that produces a chemical reaction when in contact with the solution  10  and generates the fuel gas. The solution  10  is continuously supplied to the particulate material  20  from the supply opening  10   b  at a constant rate, and the fuel gas is continuously generated by a constant rate by the chemical reaction. The size of the storage body  3  for the first chemical reaction space  30  is set so that there is no dilution of the solution concentration with the progress of the chemical reaction over time, and it is smaller than the volume of the solution storage body  1 . The chemical reaction solution further flows into the second chemical reaction space  15  through a linking opening  16 , and more gas is continuously generated here. It passes through the gas permeable material  13  and is supplied in a constant amount to the fuel cell from the gas flow space  12  and  300 .  
         [0022]      FIG. 2  is a block diagram of a hydrogen gas generation and supply device of a second embodiment of the present invention. The storage body  3  for the first chemical reaction space  3  of this second embodiment has the gas flow space  12  moved into the first storage body  3  as a flow space  30   a . Therefore, the function is the same, the same parts given the same element numbers, and duplicate descriptions omitted.  
         [0023]      FIG. 3  is a block diagram of a hydrogen gas generation and supply device of a third embodiment of the present invention. This third embodiment has a constitution where the particulate material  20  shown in  FIGS. 1 and 2  above makes contact with the solution  10  through a material  38  that limits the contact to part of the surface area. The material  38  is connected to a part that limits the infiltration rate of the solution  10  and at least one storage material having an opening in one part. Direct contact to the entire surface of the particulate material  20  is prevented, and the rate of contact with the solution  10  may be matched to the rate of the chemical reaction. Therefore, the constitution of the first solution storage body  1  is the same as the constitution of the solution storage body  1  in the first embodiment, the same parts given the same element numbers, and duplicate descriptions omitted.  
         [0024]      FIG. 4  is a block diagram of a hydrogen gas generation and supply device of a fourth embodiment of the present invention. The fourth embodiment is a device that brings about the chemical reaction and generates the gas by mixing with a second solution  20  having a prescribed concentration instead of the particulate material  20  shown in FIG. I above with the first solution  10 . Therefore, the constitution of the body  1  for the first solution storage is the same as the constitution of the solution storage body  1  in the first embodiment, the same parts given the same element numbers, and duplicate descriptions omitted.  
         [0025]     The constitution of a second solution storage body  2  is that of the solution storage body  1  and the functions thereof are the same. Therefore, the corresponding parts are each given corresponding element numbers (the one&#39;s digit being the same), and duplicate descriptions are omitted.  
         [0026]     When the first and second solutions  10  and  20  are supplied to the first chemical reaction space  30  from supply openings  10   a  and  20   a , respectively, at a constant rate, the chemical reaction occurs, and the fuel gas is generated continuously. As is shown in  FIG. 4 , this is an example where the middle of the storage body  3  of the first chemical reaction space  30  is provided with a material  33   a  with good permeability to carry out the reaction with the first and second solution storage body solution concentrations in a constant state. The storage body  3  of the first chemical reaction space  30  and the second chemical reaction spaces  15  and  25  is the same as in embodiment  1 , so duplicate descriptions are omitted.  
         [0027]      FIG. 5  is a block diagram of a hydrogen gas generation and supply device of a fifth embodiment of the present invention. The storage body  3  for the first chemical reaction space  30  in the fifth embodiment collects gas permeable materials  13  and  23  in  FIG. 4  into one as a gas flow space  13  in the space  30  in  FIG. 5  as with the storage body  3  for the first chemical reaction space  30  in  FIG. 2 . Therefore, the function is the same, the corresponding parts each given corresponding element numbers (the one&#39;s digit being the same), and duplicate descriptions omitted.  
         [0028]      FIG. 6  is a cross-sectional view of a hydrogen gas generation and supply device of a sixth embodiment of the present invention. This cross-sectional view shows the structural example in the  FIG. 3  block diagram. In the solution storage body  1 , the solution  10  having a prescribed concentration is stored in the balloon  14 , affixed to  17   c  by a ring  14   a , and the solution is supplied from the supply opening  10   b  at a constant rate to the storage body  3  for the first chemical reaction space  30  through a check valve  17 .  
         [0029]     In the storage body  3  for the first chemical reaction space  30 , a shaft pushes a ball  17   a  up from a seat  17   d  by checking the solution storage body  1  and a screw  34 , and the solution  10  is supplied at a constant rate from an outflow opening  10   b  provided deep in the center part of the chemical reaction space  30  via a narrowed part  17   b  formed from at least one indented part, from an inflow opening  10   a  and the pipe  17   c . While producing the chemical reaction with the particulate material  20  at a constant rate, this supplied solution  10  flows toward the chemical reaction space on the side of a linking pipe  16  side and flows into the second chemical reaction space  15 . Furthermore, in this  FIG. 6 , quick dissolving of the particulate material  20  through complete surface contact with the solution  10  is prevented, the storage position thereof stabilized and scattering of the particulate material  20  prevented even in usage states with the particulate material  20  at the various angles of portable use. The particulate material  20  is housed in materials  38  and  38   a  that limit the contact with the solution  10  to make the chemical reaction continuous at a constant rate. The material  38  prevents infiltration of the solution  10 , and the material  38   a  provides permeability for the solution  10 , only allowing a partial contact surface for the particulate material  20  with the solution  10 , and the contact surface of the particulate material  20  is adjusted according the chemical reaction rate. The chemical reaction solution that flows into the second chemical reaction space  15  generates more gas in that space, and it flows through the gas permeable material  13  into the gas flow space  12  and is supplied in a constant amount to the fuel cell from the outlet  300  through via paths  16   c ,  33   d  and  32 . Since a structural material  13   a  within the solution storage part  1  maintains the shape of the gas permeable material  13 , it is supported by a case  11  via a circular member  13   b  that provides a gas path on the outer periphery.  
         [0030]     The storage body for the solution storage body  1  and the first chemical reaction space  30  is sealed from the outside by a sealing material  37   b , and the first and second chemical reaction spaces  30  and  15  are sealed when the screw  34  is shut, with the chemical reaction solution only able to flow through the through hole  16 . When the solution storage body  1  and the first chemical reaction space  30  are present independently, the storage body  3  for them is affixed and held by the screw  34  using a gap provided with a seal plug for each so that the stored solution and particulate material do not leak. A gas permeable material  33  shaped by a structural material  33   a  in the same manner as the solution storage body  1  is provided in the storage body  3  for the first chemical reaction space  30 , with passage through a gas outlet  36 , but the structural member  33   a  is unnecessary.  
         [0031]      FIG. 7  is a cross-sectional view of a hydrogen gas generation and supply device of a seventh embodiment of the present invention. This seventh embodiment shows the structural example for the  FIG. 4  block diagram. As with  FIG. 6  and the  FIG. 4  block diagram, the corresponding parts in this structure are given the same element numbers and duplicate descriptions are omitted.  
         [0032]     The storage body for the first chemical reaction space  30  in this  FIG. 7  is provided with an H-shaped structural material  33   a  formed with one, two or more holes  33   b , and the constitution is such that at the periphery thereof there is an enclosure  31  provided with the gas outlet  36  via the gas permeable material  33 , gas transmission opening  33   d  and gas flow space  32 . The first and second chemical reaction solution storage bodies  1  and  2  and the first chemical reaction space  30  storage body  3  are sealed by seals  37   a  and  37   b . The solutions  10  and  20  from the balloons  14  and  24  are supplied at a constant rate in the first chemical reaction space  30  and mixed, and the gas is produced by the chemical reaction that is brought about. In this  FIG. 7 , the size of the first chemical reaction space  30  is, for example, equivalent to 1-4 cc when the required hydrogen fuel is 140-150 cc per minute with a fuel cell output of 20 watts. For that, for example, the amount of a 6% by weight concentration borohydride solution is 0.6-0.9 cc, and to keep the concentration from being diluted over time and keep the chemical reaction rate constant (room temperature and normal pressure) at this time, the outflow to the second chemical reaction space is set (factor that determines the required amount of fuel supplied from the fuel system) 2-4 minutes afterwards. However, since there is bubbling at the actual chemical reaction site for the structure in this  FIG. 6 , the 1-4 cc described previously is multiplied by 5-10, and in other words, becomes 5-40 cc, with an example on the lower limit side of 7 cc shown. Optimization of this volume is based on the overall fuel cell system that is accommodated. The volume is estimated from trial calculations of the required chemical reaction rate and corrected based on the actual structure and bubbling state of the chemical reaction. It is minimized, but it is the most important element in the present invention for making the concentration constant.  
         [0033]      FIG. 8  shows an example of a conventional gas generation and supply device for a portable fuel cell. This device is one that produces a chemical reaction, generates the gas and provides fuel to the fuel cell from the supply opening  300  by having a catalytic solution  11  a flow from a tube  22  and mix with a particulate material  21   a  when the solution storage body liquid  1  and the chemical reaction space storage body  2  are brought together at a joining part  200 . However, using this means, the chemical phenomenon is one where as the reaction time progresses, the concentration of the catalytic solution  11   a  in the chemical reaction space is diluted over time by mixing with the reacted solution, and the rate of gas production drops. Therefore, for applications with continuous production and supply of a constant amount of gas, a separate storage chamber and regulator that adjusts the supply pressure are necessary.  
         [0034]      FIG. 9  shows an example of test results on the amount of hydrogen gas generated by the present invention. The horizontal axis shows the elapsed time (in minutes) from the start of the chemical reaction of the hydrogen gas producing solution, and the vertical axis is the cumulative amount (cc) of hydrogen gas produced in that elapsed time. In the figure, curve A is an example where hydrogen gas was generated by having the chemical reaction in one space based on storage of a borohydride substance with 0.1 mole of acid at a rate of substantially 0.5 cc/min. One factor in the decrease in the hydrogen gas production rate that can be seen with the passage of time in the chemical reaction is dilution of the catalyst along with the reaction time. On the other hand, curve B is an example where 1 mole of acid and a 30% by weight borohydride solution at a rate of substantially 0.1 cc/min. were reacted first in the first reaction space (volume of approximately 5 cc), and the excess reaction liquid flowed into and stored in a second chemical reaction space having a larger volume (30 cc), with the chemical reaction continued in that space.  
         [0035]     When these curves A and B are viewed from the standpoint of chemical reaction rate, it is proof of the effect of the present invention for maintaining the concentration of the solution at the reaction site with the elapse of time based on a prescribed concentration and mixing rate even though the test conditions for curves A and B are different  
       EFFECTS OF THE EMBODIMENTS  
       [0036]     According the these embodiments, a new path may be opened seamlessly for many applications as new forms regardless of whether they are portable or stationary for the supply of fuel to fuel cells for equipment having outputs from, for example, several watts or less to over several kilowatts. Furthermore, all of the embodiments shown here may be easily developed for a variety of applications based on the main variations shown here. In addition, there is the merit that with the present device, a regulator valve that adjusts the supply gas pressure from the constant amount of gas generated is unnecessary.  
       OTHER EMBODIMENTS  
       [0037]     With the embodiments in  FIG. 1  through  FIG. 7 , it would be easy to develop applications according to the solutions used and the properties of the material for generating the fuel gas. Specifically, it is possible to mix the solution using a constant rate where the balloon function is replaced by gravity, for example, for operation in a fixed state for stationary applications. In, for example, the case of a fuel cell with a 20 watt chamber power within the reaction space, combining the mixture and chemical reaction rate, a structure where a first chemical reaction space with a hanging bell shape of at least one hydrophilic material cluster of a size of 10-20 mm in diameter or on one side and layered vertically is chemically reacted while falling and after passing through that space is further stored in a second chemical reaction space below it and gas continuously generated is not shown in the drawings, but it has the same concept.  
         [0038]     Furthermore, even if the solution storage body  1  and the storage body  3  for the first chemical reaction space are in a state joined by the screw  34  in  FIG. 5 , it is easy to make the shaft  17   e  movable from the outside of the case  31  through the sealing material by manually pushing the ball  17   a  upwards when fuel gas is necessary. In addition, it is naturally possible to apply the use of the present invention to production of gases other than hydrogen. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0039]      FIG. 1  is a block diagram of a hydrogen gas generation and supply device that makes the chemical reaction rate for the particulate material constant in a first embodiment of the present invention.  
         [0040]      FIG. 2  is a block diagram (embodiment 2) where the gas flow space in  FIG. 1  is moved to the first chemical reaction space.  
         [0041]      FIG. 3  is a block diagram (embodiment 3) where there is provided a solution infiltration material for limiting the chemical reaction surface area of the particulate material in  FIG. 1 .  
         [0042]      FIG. 4  is a block diagram (embodiment 4) of a hydrogen gas generating and supply device that makes the chemical reaction rate for a solution constant instead of the particulate material of  FIG. 1 .  
         [0043]      FIG. 5  is a block diagram (embodiment 5) where the gas flow space in  FIG. 3  is moved to the first chemical reaction space.  
         [0044]      FIG. 6  is a cross-sectional view (embodiment 1 block diagram) showing a structural example for  FIG. 1 .  
         [0045]      FIG. 7  is a cross-sectional view (embodiment 4 block diagram) showing a structural example for  FIG. 4 .  
         [0046]      FIG. 8  is a diagram of production of a constant amount of hydrogen showing an example of test results using the present invention.  
         [0047]      FIG. 9  is a cross-sectional diagram showing a conventional hydrogen gas generation and supply device for portable fuel cells.  
       EXPLANATION OF THE ELEMENTS  
       [0048]     In the drawings,  
         [0049]      1 ,  2  chemical reaction solution storage body  
         [0050]      3  chemical reaction space storage body  
         [0051]      10 ,  20  chemical reaction solution  
         [0052]      14 , 24  balloon  
         [0053]      13 ,  23 ,  33 ,  33   e  gas permeable material  
         [0054]      13   a ,  23   a ,  33   a  structural material forming gas transmitting film  
         [0055]      10   a ,  20   a  solution supply opening  
         [0056]      16 ,  26  chemical reaction solution outlet  
         [0057]      17   d ,  18 ,  27   d ,  28 ,  37   a ,  37   b  sealing material  
         [0058]      17   b ,  27   b  narrowed part  
         [0059]      17 ,  27  check valve  
         [0060]      17   a ,  27   a  ball  
         [0061]      17   e ,  27   e  shaft  
         [0062]      15 ,  25 ,  30  chemical reaction space  
         [0063]      12 ,  16   c ,  22 ,  26   c ,  30   b ,  32 ,  33   d  gas flow space  
         [0064]      11 ,  21 ,  31  casing  
         [0065]      16   b ,  26   b ,  30   b  gas permeable part  
         [0066]      33   c  shaft support part  
         [0067]      14   a ,  24   a  balloon holding ring  
         [0068]      13   b ,  23   b  peripheral grooved ring  
         [0069]      34 ,  35  storage body connecting screw part  
         [0070]      38 ,  38   a  solution permeation limiting material  
       DOCUMENT NAME: DRAWINGS  
       [0071]    
       FIG. 1 
     
         [0072]    
       FIG. 2 
     
         [0073]    
       FIG. 3 
     
         [0074]    
       FIG. 4 
     
         [0075]    
       FIG. 5 
     
         [0076]    
       FIG. 6 
     
         [0077]    
       FIG. 7 
     
         [0078]    
       FIG. 8 
     
         [0079]    
       FIG. 9