The present invention relates to a fuel cell system provided with a fuel generation unit.
In a fuel cell, a cell typically has a structure where a solid polyelectrolyte membrane which employs a solid polymer ion exchange membrane, a solid oxide electrolyte membrane which employs yttria-stabilized zirconia (YSZ), or the like is sandwiched between a fuel electrode (anode) and an oxidant electrode (cathode). Such a cell is further provided with a fuel gas flow passage to supply a fuel gas (such as hydrogen gas) to the fuel electrode and an oxidizing gas flow passage to supply an oxidizing gas (such as oxygen gas or air) to the oxidant electrode, and power is generated with the fuel gas and the oxidizing gas supplied through these flow passages to the fuel electrode and the oxidant electrode, respectively.
Since the fuel cell is theoretically capable of generating electric energy at a high efficiency, it contributes to saving energy, and the fuel cell also provide a highly eco-friendly power generating method, and thus the fuel cell is expected as a very powerful solution to energy and environmental problems on a global scale.
Patent Literature 1 WO2011/040182
Patent Literature 2 WO2011/052283
As a secondary battery type fuel cell system which is capable of generating power and rechargeable, there has been proposed a system where a fuel electrode and a fuel generating member are disposed in a sealed space, and reactions are promoted by natural diffusion (see Patent Literature 1 and Patent Literature 2). With natural diffusion, however, a speed of reaction with a fuel gas is limited, and this disadvantageously prevents the fuel cell from outputting high power. Here, it is desirable that this problem be solved while improving a fuel cell generating efficiency as high as possible.
In view of the above-mentioned situation, an object of the present invention is to provide a fuel cell system that is capable of achieving both high output and high fuel generating efficiency.
To achieve the above object, a fuel cell system according to the present invention includes a fuel generation unit that generates a fuel through a chemical reaction; a fuel cell unit that performs power generation by using the fuel supplied from the fuel generation unit; a circulation unit that forcibly circulates gas that includes the fuel or a product of the power generation between the fuel generation unit and the fuel cell unit; and a control unit that controls the circulation unit. Here, the control unit periodically changes a flow rate of the gas that is made to circulate by the circulation unit.
According to a fuel cell system of the present invention, it is possible to achieve both high output and high fuel cell generating efficiency.
Embodiments of the present invention will be described below with reference to accompanying drawings. It should be noted that the present invention is not limited to the embodiments described below.
As a material of the fuel generation unit 1, for example, there can be used one that has a metal as a base material and is formed adding a metal or a metal oxide to the base material, that generates a fuel (such as hydrogen) through an oxidation reaction with an oxidizing gas (such as water vapor), and that can be recovered through a reduction reaction with a reducing gas (such as hydrogen). Examples of the metal for the base material include, for example, Ni, Fe, Pd, V, Mg, and an alloy of any of these metals, and in particular, Fe is preferable because of its low cost and workability. Examples of the metal to be added include Al, Rh, Pd, Cr, Ni, Cu, Co, V, and Mo, and examples of the metal oxide to be added include SiO2 and TiO2. It should be noted that the metal for the base material and the metal to be added are different metals. In the present embodiment, as the fuel generation unit 1, a fuel generating member composed mainly of Fe is employed.
The fuel generating member composed mainly of Fe is capable of consuming water vapor as the oxidizing gas and generating hydrogen gas as the fuel (the reducing gas) through an oxidation reaction shown in formula (1) below.
4H2O+3Fe→4H2+Fe3O4 (1)
With progress of the oxidation reaction of Fe of formula (1) above, change of iron into iron oxide progresses to gradually reduce an amount of remaining iron, but through a reaction reverse to the reaction shown in formula (1), that is, a reduction reaction shown in formula (2) below, the fuel generation unit 1 can be recovered. Note that the oxidation reaction of Fe shown in formula (1) above and the reduction reaction shown in formula (2) below are both able to be performed even at a low temperature such as a temperature lower than 600° C.
4H2+Fe3O4→3Fe+4H2O (2)
In the fuel generation unit 1, a large surface area per unit volume of the fuel generation unit 1 is desirable for higher reactivity of the fuel generation unit 1. A measure to increase the surface area of the fuel generation unit 1 per unit volume is, for example, to break the main material of the fuel generation unit 1 into fine particles and mold the fuel generation unit 1 out of the fine particles. An example of method to make such fine particles is crushing by using, for example, a ball mill. Moreover, the surface area of the fine particles may be further increased by generating cracks by, for example, a mechanical method, or alternatively, the surface area of the fine particles may be further increased by roughening the surface of the fine particles by a method such as acid treatment, alkali treatment, and blasting. The fuel generation unit 1 may be one that is formed by compressing the fine particles with air space that is large enough to allow passage of gas left among the fine particles, or alternatively, the fuel generation unit 1 may be one that is formed by arranging in a space a large number of pellets made of the fine particles.
The fuel cell unit 2 is, as shown in
The circulation unit 3 is provided to forcibly circulate gas between the fuel generation unit 1 and the fuel cell unit 2 in a direction indicated by an arrow shown in
The container 6 includes a circulation gas supply port for supplying circulation gas to the fuel electrode 2B, a circulation gas discharge port for discharging the circulation gas from the fuel electrode 2B, an air supply port for supplying air to the air electrode 2C, and an air discharge port for discharging the air from the air electrode 2C. The flow of air may be controlled, for example, by using a fan or the like disposed outside the container 6. It should be noted the air-flow direction is not limited to the direction shown in
The container 7 includes a circulation gas supply port for supplying the circulating gas to the fuel generation unit 1 and a circulation gas discharge port for discharging the circulating gas from the fuel generation unit 1.
The control unit 9 periodically changes a flow rate of gas circulated by the circulation unit 3. The flow rate of gas herein means an amount (volume) of gas that flows through a fixed cross-section in a unit period of time, and can be measured by using a flow meter. In the present embodiment, the control unit 9 periodically changes the flow rate of the gas circulated by the circulation unit 3 by repeated alternate use of two flow rates. For example, in a case where the circulation unit 3 is a fan, the control unit 9 may perform ON/OFF control of the fan, or may alternately switch a rotation speed of the fan between two speeds. Furthermore, for example, when the circulation unit 3 is a diaphragm circulator, the control unit 9 may alternately switch a modification cycle of the diaphragm between two phases.
As a material of the electrolyte membrane 2A, for example, a solid oxide electrolyte using yttria-stabilized zirconia (YSZ) can be used, or alternatively, for example, a solid polyelectrolyte, such as Nafion (a trademark of E. I. du Pont de Nemours & Co.), a cation conductive polymer, and an anion conductive polymer, can be used; however, the material of the electrolyte membrane 2A is not limited to these materials, and any material may be used as long as it has all the characteristics required to be the electrolyte of the fuel cell, such as a material that transmits hydrogen ions or oxygen ions, and a material that transmits hydroxide ions. The present embodiment uses, as the electrolyte membrane 2A, an electrolyte that transmits oxygen ions or hydroxide ions, such as a solid oxide electrolyte using yttria-stabilized zirconia (YSZ).
In a power generation operation, a switch SW1 is turned ON and a switch SW2 is turned OFF, to thereby electrically connect the fuel cell unit 2 to a load 11.
For example, in a case where hydrogen is used as the fuel, in the present embodiment, in the power generation operation, a reaction shown in formula (3) below takes place at the fuel electrode 2B.
H2+O2−→H2O+2e− (3)
Electrons generated by the reaction shown in formula (3) above move from the fuel electrode 2B, to pass through the load 11, and reach the air electrode 2C, where a reaction shown in formula (4) below takes place.
½O2+2e−→O2− (4)
Subsequently, oxygen ions generated through the reaction shown in formula (4) above move to pass through the electrolyte membrane 2A, and reach the fuel electrode 2B. By repeating the above series of reactions, the fuel cell unit 2 performs the power generation operation.
And, through the oxidation reaction of Fe shown in formula (1) above, the fuel generation unit 1 consumes water vapor supplied from the fuel cell unit 2, generates a hydrogen gas, and supplies the hydrogen gas to the fuel cell unit 2.
Note that the fuel cell system according to the one embodiment of the present invention shown in
The electrolyte membrane 2A can be produced by using, for example, a chemical vapor deposition-electrochemical vapor deposition (CVD-EVD) method in the case where a solid oxide electrolyte is employed, and in the case where a solid polyelectrolyte is employed, the electrolyte membrane 2A can be produced by using, for example, a coating method.
The fuel electrode 2B and the air electrode 2C may each have a structure, for example, that includes a catalyst layer in contact with the electrolyte membrane 2A and a diffusion electrode laid on the catalyst layer. As the catalyst layer, for example, one that is constituted with carbon black supporting platinum black or a platinum alloy thereon may be used. As a material of the diffusion electrode of the fuel electrode 2B, carbon paper, an Ni—Fe cermet, an Ni—YSZ cermet, etc. can be used, for example. As a material of the diffusion electrode of the air electrode 2C, carbon paper, an La—Mn—O compound, an La—Co—Ce compound, etc. can be used, for example. The fuel electrode 2B and the air electrode 2C can each be formed, for example, by using a vapor-deposition method or the like.
In the fuel cell system according to the one embodiment of the present invention, since the fuel gas is forcibly circulated by the circulation unit 3, the fuel gas flows at a higher speed in comparison with a case of natural diffusion, and this accordingly makes it possible to supply the fuel electrode 2B with an ample amount of fuel to be used in the reaction that takes place at the fuel electrode 2B. This contributes to larger output compared with the case of natural diffusion.
In the fuel cell system according to the one embodiment of the present invention, the flow rate of the gas circulated by the circulation unit 3 is periodically changed, and thereby pressure pulsation of gas is generated, and the pressure pulsation of gas is propagated from the circulation unit 3 to the fuel generation unit 1. This helps improve the efficiency of the fuel generation performed by the generation unit 1. Reason why the efficiency of the fuel generation is improved this way will be described in detail with reference to
In the present embodiment, since the pressure pulsation of gas is propagated from the circulation unit 3 to the circulation gas supply port of the container 7, gas dispersion due to pressure difference caused by the pressure pulsation arises all over inside the container 7 as shown in
Instead of forming the fuel generation unit 1 with a plurality of pellets, the fuel generation unit 1 may be constituted with, for example, a molded body 14 having a plurality of gas flow passages formed therein as shown in
Since the molded body 14, which constitutes the fuel generation unit 1, is a porous body, gas can permeate into the molded body 14, where flow resistance is larger than in the gas flow passages. Thus, with the feature of the present embodiment, in the case where the fuel generation unit 1 is constituted with a molded body, too, the propagation of pressure pulsation helps gas to permeate into the molded body where flow resistance is large, and reactions inside the molded body contribute to improvement of the fuel generating efficiency.
Further, in comparison between a case of periodically changing the flow rate of the gas circulated by the circulation unit 3 and a case of setting the flow rate of the gas circulated by the circulation unit 3 to a fixed rate, assuming generating the same amount of fuel in both cases, as shown in
As mentioned above, in the case where the flow rate of the gas circulated by the circulation unit 3 is set to a fixed rate, the circulation gas flows only through places with small resistance as shown in
In contrast, in the case where the flow rate of the gas circulated by the circulation unit 3 is periodically changed, as mentioned above, gas dispersion takes place all over as shown in
Next, examples of control by the control unit 9 will be described.
The control unit 9 controls the circulation unit 3 such that the flow rate of the gas circulated by the circulation unit 3 periodically changes as shown in
The cases shown in
The volume of the fuel generation unit 1 changes each time the oxidation reaction shown in formula (1) above and the reduction reaction shown in formula (2) above take place, and along with such volume change of the fuel generation unit 1, some of the fine particles, which are mainly Fe, come off from the pellets, the molded body, or the like, and such fine particles may collect in, for example, areas enclosed by dotted lines in
To prevent this, the control unit 9 may perform control, for example, such that the difference between the two flow rates becomes larger than usual at regular time intervals as shown in
In some cases, in order to prevent fine particles from the pellets, the molded body, or the like of the fuel generation unit 1 from polluting the fuel cell unit 2, a filter 15 that captures fine particles is disposed between a circulation gas flow-out side of the fuel generation unit 1 and a circulation gas flow-in side of the fuel cell unit 2 as shown in
The control unit 9 may have a first control mode where the flow rate of the gas circulated by the circulation unit 3 is periodically changed and a second control mode where the flow rate of the gas circulated by the circulation unit 3 is set to a fixed flow rate, such that the control unit 9 switches between the first and second control modes as shown in
The control unit 9 may change the difference between the two flow rates for the purpose of changing the output of the fuel cell unit 2 in response to change in electric power required by an external load. When the control unit 9 changes the difference between the two flow rates, this change is followed by change in amount of fuel generated in the fuel generation unit 1, as a result of which the output of the fuel cell unit 2 is changed (see
In a case where clogging is caused in the gas flow passages by fine particles coming off from the pellets, the molded body, or the like of the fuel generation unit 1, the output of the fuel cell unit 2 sharply declines in a short period of time. Therefore, the control unit 9 may acquire output information of the fuel cell unit 2 such that, in the case where the output of the fuel cell unit 2 has sharply declined in a short period of time, the control unit 9 performs control to increase the difference between the two flow rates, and when fine particles clogging the gas flow passages have moved to where the fine particles do not clog any gas flow passage and the output of the fuel cell unit 2 has been recovered, the control unit 9 performs control to bring the difference between the two flow rates back to usual (see
In the control example shown in
In the present control example, it is preferable that the control unit 9 store information defining “sharply” and “short period of time” mentioned above (for example, a threshold rate-of-change of the output of the fuel cell unit 2). For example, control may be performed such that, in a case where the rate of the output of the fuel cell unit 2 to energy fed to the circulation unit 3 in a set period of time has fallen equal to or lower than half the rate of a directly previous set period of time, the output is determined to have sharply declined in a short period of time, and the difference between the two flow rates is made larger than usual.
At the fuel generation unit 1, when an amount of remaining fuel (rate of unoxidized fuel) reduces, the fuel generating efficiency is lowered to cause a decrease in amount of fuel generated at the fuel generation unit 1. Thus, if operation is continued without changing the amount of the gas circulated by the circulation unit 3, the output of the fuel cell unit 2 is lowered. To prevent this, in the present control example, the control unit 9 increases the amount of fuel generation by gradually increasing the difference between the two flow rates according to decrease in amount of fuel remaining in the fuel generation unit 1, to thereby make up for the lowered fuel generating efficiency (see
In the present embodiment, advisably, the control unit 9 acquires a result of detection performed by a remaining fuel amount detecting unit which detects the amount of fuel remaining in the fuel generation unit 1. Examples of the remaining fuel amount detecting unit mentioned above include a device that detects a recovery state of the fuel generation unit 1 on a basis of change in weight of the fuel generation unit 1, and a device that detects the recovery state of the fuel generation unit 1 on a basis of change in magnetic permeability of the fuel generation unit 1 in a case where the fuel generation unit 1 is made of Fe as in the present embodiment. The remaining fuel amount detecting unit may be disposed inside the fuel cell system, or may be disposed outside the fuel cell system.
In the case where the two flow rates are alternately repeated as described above, it is desirable to control the larger flow rate to be larger than the value of the gas flow rate adopted in a case where the gas flow rate is fixed to a constant value (normally, a value obtained by adding some margin to the gas flow rate necessary to generate a required amount of fuel), and control the smaller flow rate to be smaller than the value of the fixed gas flow rate.
In the above embodiments, two flow rates are alternately repeated, but this is not meant as a limitation, and more than two flow rates may be adopted in combination as long as it is able to generate pressure pulsation of gas.
In each of the above embodiments, a solid oxide electrolyte is used as the electrolyte membrane 2A of the fuel cell unit 2, such that water is generated on the fuel electrode 2B side in power generation. With this structure, only a passage that transmits water generated on the fuel electrode 2B side to the fuel generation unit 1 and a passage that transmits fuel from the fuel generation unit 1 to the fuel electrode 2B are required, and this is advantageous to achieve simple and compact devices. On the other hand, as in the fuel cell disclosed in JP-A-2009-99491, it is also possible to use a solid polyelectrolyte that transmits hydrogen ions as the electrolyte membrane 2A of the fuel cell unit 2. In this case, since water is generated in power generation on the side of the air electrode 2C which is the oxidant electrode of the fuel cell unit 2, it is necessary to additionally provide a flow passage that transmits the thus generated water to the fuel generation unit 1. Furthermore, instead of making one fuel cell unit 2 perform both power generation and electrolysis of water as in the above embodiments, there may be adopted a structure where a fuel cell (such as a solid oxide fuel cell dedicated to power generation) and a water electrolysis unit (such as a solid oxide fuel cell dedicated to electrolysis of water) are parallelly connected to the fuel generation unit 1 on the gas flow passage.
Moreover, instead of using hydrogen as the fuel for the fuel cell unit 2 as in the above embodiments, a reducing gas other than hydrogen gas, such as carbon monoxide gas and hydrocarbon gas, may be used as the fuel for the fuel cell unit 2.
Furthermore, instead of using air as the oxidizing gas as in the above embodiments, oxidizing gas other than air may be used.
Number | Date | Country | Kind |
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2012-084979 | Apr 2012 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2013/059170 | 3/28/2013 | WO | 00 |