(19)
(11)EP 3 322 014 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
17.06.2020 Bulletin 2020/25

(21)Application number: 15897713.2

(22)Date of filing:  08.07.2015
(51)International Patent Classification (IPC): 
H01M 8/04(2016.01)
H01M 8/0612(2016.01)
H01M 8/249(2016.01)
H01M 8/1213(2016.01)
H01M 8/12(2016.01)
H01M 8/0637(2016.01)
H01M 4/86(2006.01)
H01M 8/124(2016.01)
(86)International application number:
PCT/JP2015/069594
(87)International publication number:
WO 2017/006450 (12.01.2017 Gazette  2017/02)

(54)

FUEL CELL SYSTEM

BRENNSTOFFZELLENSYSTEM

SYSTÈME DE PILES À COMBUSTIBLE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(43)Date of publication of application:
16.05.2018 Bulletin 2018/20

(73)Proprietor: Nissan Motor Co., Ltd.
Yokohama-shi, Kanagawa 221-0023 (JP)

(72)Inventors:
  • YAGUCHI, Tatsuya
    Atsugi-shi Kanagawa 243-0123 (JP)
  • KAMIJO, Motohisa
    Atsugi-shi Kanagawa 243-0123 (JP)

(74)Representative: Grünecker Patent- und Rechtsanwälte PartG mbB 
Leopoldstraße 4
80802 München
80802 München (DE)


(56)References cited: : 
EP-A2- 1 441 406
JP-A- H05 325 996
JP-A- 2009 021 195
JP-A- 2011 525 295
JP-A- 2013 211 107
US-A1- 2007 015 015
JP-A- H0 745 293
JP-A- 2008 305 600
JP-A- 2010 282 772
JP-A- 2012 531 719
JP-A- 2014 229 438
US-A1- 2013 014 484
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention relates to a fuel cell system which supplies fuel and oxidizer to a fuel cell and causes it to generate electric power.

    BACKGROUND ART



    [0002] A general solid-oxide type fuel cell uses an oxide ion conductive material as electrolyte and requires an operating temperature of 500°C or more to obtain ion conductivity. Accordingly, the solid-oxide type fuel cell, which requires warm-up time in the case of cold-start, has been conventionally used mainly for stationary equipment with a low frequency of cold-start.

    [0003] Accordingly, in view of adapting the aforementioned fuel cell to a mobile body, there has been proposed a multi-stage fuel cell system having small fuel cells and large fuel cells in order to support both quick startability and high output required for a mobile body (see European Patent Publication No. 1507302).

    [0004] US 2013/014484 A1 discloses a fuel cell system according to the preamble of independent claim 1. EP 1441406 A discloses a fuel cell including at least one electrode operatively disposed in the fuel cell, and having a catalytically active surface. The fuel cell further includes a mechanism for maintaining a substantially uniform maximum catalytic activity over the surface of the electrode.

    SUMMARY OF INVENTION



    [0005] When a conventional multi-stage fuel cell system described above has a plurality of fuel cells piping-connected in series, a fuel cell on the first stage causes a large endothermic reaction (steam reforming reaction: CH4+H2O → 3H2+CO) when generating electric power, due to a large amount of methane included in the fuel reformed by a reformer located upstream thereof. Accordingly, the fuel cell on the first stage, despite generating heat, results in temperature drop which leads to decreased efficiency of electric power generation due to the large endothermic reaction.

    [0006] Thus, it is an object of the present invention to suppress the decrease in the electric power generation efficiency of the fuel cell system having a plurality of fuel cells arranged in series.

    [0007] The object is achieved with the fuel cell system according to independent claim 1. In a fuel cell system according to the present disclosure, the fuel cell on the first stage, among a plurality of fuel cells connected to each other in series, has a methane reaction suppressing function which suppresses reaction of methane included in reformed fuel to a larger extent than at least one of the fuel cells on the second and later stages.

    BRIEF DESCRIPTION OF DRAWINGS



    [0008] 

    [Fig. 1] Fig. 1 is an overall configuration diagram of a fuel cell system according to a first embodiment of the present invention.

    [Fig. 2] Fig. 2 is a schematic plan view illustrating a reaction region of fuel cells in the fuel cell system of Fig. 1, in which Fig. 2(a) illustrates a fuel cell on the first stage and Fig. 2(b) illustrates a fuel cell on the second stage.

    [Fig. 3] Fig. 3 illustrates a methane reaction suppressing function of the first embodiment, in which Fig. 3(a) is a schematic cross-sectional view of an electrolyte and fuel poles of the fuel cell on the first stage and Fig. 3(b) is a schematic cross-sectional view of an electrolyte and fuel poles of the fuel cell on the second stage.

    [Fig. 4] Fig. 4 is a graph illustrating the amount of generated heat when the fuel cell on the first stage is provided with the methane reaction suppressing function.

    [Fig. 5] Fig. 5 is a graph illustrating the amount of generated heat when the fuel cell on the first stage is not provided with the methane reaction suppressing function as a comparative example.

    [Fig. 6] Fig. 6 illustrates a methane reaction suppressing function of a second embodiment, in which Fig. 6(a) is a schematic cross-sectional view of an electrolyte and fuel poles of the fuel cell on the first stage and Fig. 6(b) is a schematic cross-sectional view of electrolyte and fuel poles of the fuel cell on the second stage.

    [Fig. 7] Fig. 7 illustrates a methane reaction suppressing function of a third embodiment, in which Fig. 7(a) is a schematic cross-sectional view of an electrolyte and fuel poles of the fuel cell on the first stage and Fig. 7(b) is a schematic cross-sectional view of an electrolyte and fuel poles of the fuel cell on the second stage.

    [Fig. 8] Fig. 8 illustrates a methane reaction suppressing function of a fourth embodiment and is an explanatory diagram illustrating an example in which the thickness of fuel poles of a fuel cell on a later stage is made thicker than that of preceding stages.

    [Fig. 9] Fig. 9 illustrates a methane reaction suppressing function of a fifth embodiment, and is an explanatory diagram illustrating an example in which, with regard to the composition ratio between a proton conductive material, which is supposed to be the material of electrolyte, and an oxide conductive material, the proportion of the proton conductive material of a fuel cell on a later stage is made lower than that on preceding stages.

    [Fig. 10] Fig. 10 illustrates a methane reaction suppressing function of a sixth embodiment and is an explanatory diagram illustrating an example in which a discharged fuel reformer is provided between fuel cells which are adjacent to each other among a plurality of fuel cells.

    [Fig. 11] Fig. 11 is an overall configuration diagram of a fuel cell system according to a seventh embodiment.


    DESCRIPTION OF EMBODIMENTS



    [0009]  Hereinafter, embodiments for implementing the present invention will be described in detail with reference to the drawings.

    [0010] Fig. 1 is an overall configuration diagram of a fuel cell system common to respective embodiments described below. A first fuel cell 1 on the first stage and a second fuel cell 3 on the second stage in a fuel cell system are solid-oxide type fuel cells (SOFC). The first and the second fuel cells 1 and 3 have respectively supplied thereto hydrogen as fuel and air as oxidizer to generate electric power.

    [0011] The first and the second fuel cells 1 and 3 have a plurality of cells stacked to form fuel cell stack. One cell includes electrolyte, a fuel pole, an oxygen pole, a fuel-pole-side separator forming a fuel-flow path, and an oxygen-pole-side separator forming an air-flow path.

    [0012] The first fuel cell 1 is smaller in electric power generation capacity and size than the second fuel cell 3. In order to downsize the first fuel cell 1, the area of a reaction (electric power generation) region S1 of an electrode of the first fuel cell 1 indicated by slant lines is made smaller than a reaction (electric power generation) region S2 of an electrode of the second fuel cell 3 indicated by slant lines, as illustrated in Fig. 2. When stacking fuel cells, the first fuel cell 1 is made smaller than the second fuel cell 3 in terms of the total area of reaction regions of all of the plurality of cells.

    [0013] The first fuel cell 1 and the second fuel cell 3 are connected to each other in series via a fuel piping 5 and an air piping 7. In other words, a plurality of fuel cells is connected to each other in series. The first fuel cell 1 is located upstream side to the second fuel cell 3 in the flow of fuel and air.

    [0014] A fuel supply piping 11 connecting the first fuel cell 1 and a fuel tank 9 has provided thereon a fuel pump 13, a carburetor 15, a heat exchanger 17, and a reformer 19, respectively, in the order from side of the fuel tank 9. Raw fuel in the fuel tank 9 includes hydrocarbon-based fuel such as gasoline, light oil or kerosene, or alcohol-based liquid fuel such as methanol or ethanol.

    [0015] The fuel pump 13 sends liquid fuel from the fuel tank 9 to the carburetor 15. The carburetor 15 turns the raw fuel into sprayed mist by ejecting liquid fuel from an unillustrated nozzle, for example, and by ejecting the pressurized liquid fuel from micropores of the nozzle. Furthermore, a combustor 21 is connected to the carburetor 15 via a combustion exhaust pipe 22, and the sprayed mist of raw fuel is vaporized using the exhaust heat of the combustor 21. The heat exchanger 17 uses the combustor 21 to exchange heat with, and raise the temperature of, the raw fuel vaporized by the carburetor 15.

    [0016] The combustor 21 and the second fuel cell 3 are connected to each other via a fuel discharge pipe 23 and an air discharge pipe 25. In other words, discharged fuel discharged from the second fuel cell 3 is supplied to the combustor 21 through the fuel discharge pipe 23, and discharged air discharged from the second fuel cell 3 is supplied to the combustor 21 through the air discharge pipe 25. The combustor 21 performs combustion using the supplied discharged fuel and discharged air as the raw fuel.

    [0017] An air supply piping 29 connecting the first fuel cell 1 and an air compressor 27 has provided thereon a first air heat exchanger 31 and a start-up combustor 33, respectively, in the order from the air compressor 27 side. The air compressor 27 sends fresh air (air) to the first air heat exchanger 31. The first air heat exchanger 31 raises the temperature of air sent from the air compressor 27 by exchanging heat with combustion gas supplied via the combustion exhaust pipe 22 described above. The exhaust air exhausted from the first air heat exchanger 31 is exhausted outside via an exhaust muffler 35.

    [0018] The start-up combustor 33 is connected to the fuel tank 9 via an unillustrated fuel piping and combusts liquid fuel supplied thereto from the fuel tank 9 by a fuel pump 37. The air sent to the start-up combustor 33 from the first air heat exchanger 31 is heated by combustion heat of the start-up combustor 33 whereby its temperature rises.

    [0019] The air supply piping 29 between the air compressor 27 and the first air heat exchanger 31 has an air manifold 39 connected thereto in a branched manner. The air manifold 39 is further branched into a second air supply piping 41 and an air mixing pipe 43.

    [0020] The second air supply piping 41, having a second air heat exchanger 45 provided midway thereof, is connected to the air piping 7. In the second air heat exchanger 45, exhaust heat flowing through the combustion exhaust pipe 22 heats and raises the temperature of air, and the air with raised temperature is supplied to the second fuel cell 3. The air mixing pipe 43 has the fuel supply piping 11 connected between the carburetor 15 and the heat exchanger 17, which mixes the air sent from the air compressor 27 with the raw fuel flowing through the fuel supply piping 11.

    [0021] The fuel cell system configured as described above operates in the following manner.

    [0022] Liquid fuel is sent from the fuel tank 9 to the carburetor 15 by the fuel pump 13, and further, vaporized raw fuel is sent to the reformer 19 via the heat exchanger 17. On this occasion, a part of the air sent from the air compressor 27 is mixed into raw fuel in the fuel supply piping 11 through the air manifold 39 and the air mixing pipe 43, and subsequently sent to the reformer 19 via the heat exchanger 17.

    [0023] The reformer 19 decomposes the raw fuel and also the water and air mixed in the raw fuel at a high temperature, and reforms them into constituents such as H2, CH4, CO, CO2, H2O, and the reformed fuel is supplied to the first fuel cell 1. On the other hand, the air sent from the air compressor 27 has its temperature raised through the first air heat exchanger 31 and the start-up combustor 33, and is supplied to the first fuel cell 1.

    [0024] The first fuel cell 1 generates electric power utilizing the reaction between the reformed fuel supplied thereto and oxygen, which is the oxidizer in the atmosphere. The first fuel cell 1 is smaller in electric power generation capacity and size than the second fuel cell 3, and therefore is activated in a shorter time. Subsequent to electric power generation by the first fuel cell 1, surplus fuel and air are supplied to the second fuel cell 3 respectively through the fuel piping 5 and the air piping 7. On this occasion, a part of the air from the air compressor 27 is supplied to the second fuel cell 3 through the air manifold 39 and the second air supply piping 41.

    [0025] The second fuel cell 3 generates electric power utilizing the reaction between the supplied fuel and oxygen which is the oxidizer in the atmosphere. Subsequent to electric power generation by the second fuel cell 3, surplus fuel and air are supplied for combustion to the combustor 21 respectively through the fuel discharge pipe 23 and the air discharge pipe 25.

    [0026] Application to an automobile, among mobile bodies, requires support of both quick startability and high output. Accordingly, the total reaction area of the first fuel cell 1 on the first stage is made smaller than the total reaction area of the second fuel cell 3 on the second stage, so as to reduce the heat capacity of the first fuel cell 1 on the first stage. While realizing quick startability by the first fuel cell 1 with reduced heat capacity, a large output is obtained from electric power generation by the two fuel cells 1 and 3 after having activated the second fuel cell 3. Accordingly, there may be provided a fuel system suitable for an automobile.

    [0027] The first fuel cell 1 with reduced heat capacity generates a small amount of heat when generating electric power, and is therefore effective for suppressing temperature drop by providing a methane reaction suppressing function described below to suppress the amount of absorbed heat so that the amount of absorbed heat does not exceed the amount of generated heat.

    [0028] Next, respective embodiments will be described in which the first fuel cell 1 on the first stage is provided with a methane reaction suppressing function.

    [0029] Fig. 3 illustrates a methane reaction suppressing function of a first embodiment. Fig. 3(a) illustrates a schematic cross-sectional view of an electrolyte 47A and fuel poles 49A of a first fuel cell 1A on the first stage, and Fig. 3(b) illustrates a schematic cross-sectional view of an electrolyte 51A and fuel poles 53A of a second fuel cell 3A on the second stage.

    [0030] In both of the fuel cells 1A and 3A, the fuel poles 49A and 53A include Ni (nickel) and YSZ (yttria-stabilized zirconia). The electrolytes 47A and 51A include YSZ.

    [0031] The first embodiment is intended to provide the first fuel cell 1A with a methane reaction suppressing function by making the thickness T1 of the fuel poles 49A in the first fuel cell 1A on the first stage thinner than the thickness T2 of the fuel poles 53A in the second fuel cell 3A on the second stage. The respective thicknesses T1 and T2 of the fuel poles 49A and 53A correspond to the thickness of a part where a three-phase interface is formed at which hydrogen ions, electrons and fuel gas adjoin each other. The aforementioned hydrogen ions, electrons and fuel gas can be respectively replaced by electrolyte (liquid phase), fuel poles (solid-phase) and hydrogen (gas phase).

    [0032] It is known that thinning the thickness of fuel poles causes increase of local current density and, on this occasion, hydrogen reaction activity tends to be higher than methane. Therefore, reaction of methane can be suppressed when the first fuel cell 1A on the first stage generates electric power. Accordingly, the first fuel cell 1A can suppress the amount of absorbed heat during steam reforming reaction (endothermic reaction), even when a large amount of methane is included in the fuel reformed by the reformer 19.

    [0033] Therefore, the first fuel cell 1A can cause the amount of generated heat to exceed the amount of absorbed heat, thereby securing the temperature required for stable operation. As a result, it is possible to suppress decrease of the electric power generation efficiency in the fuel cell system.

    [0034] In this case, it becomes unnecessary to introduce a more-than-required amount of air into raw fuel to reduce methane during reforming, or heat the air for electric power generation beyond the operating temperature of the first fuel cell 1A on the first stage, in order to appropriately maintain the temperature of the first fuel cell 1A on the first stage. As a result, it is possible to suppress decrease of the electric power generation efficiency of the fuel cell system.

    [0035] Methane whose reaction is suppressed at the first fuel cell 1A on the first stage turns out to be used by reacting during electric power generation by the second fuel cell 3A on the later stage with increased thickness of the fuel poles 53A, thereby allowing effective use of injected fuel.

    [0036] Fig. 4 illustrates an amount of generated heat by injected fuel in a case where the first fuel cell 1A according to the first embodiment is provided with a methane reaction suppressing function, and Fig. 5 illustrates an amount of generated heat by injected fuel in a case where the fuel cell on the first stage is not provided with a methane reaction suppressing function as a comparative example.

    [0037] In Fig. 5 illustrated as a comparative example, the amount of generated heat by the injected fuel, which is heating the air for electric power generation, is larger than that of the present embodiment of Fig. 4 by approximately the amount denoted H (1.4 kW). This is because the amount of absorbed heat (0.58 kW) due to the large amount of methane reaction in the fuel cell on the first stage exceeds the amount of generated heat (0.32 kW).

    [0038] In the present embodiment of Fig. 4, methane reaction is suppressed in the first fuel cell 1A and therefore a large endothermic reaction such as that illustrated in Fig. 5 is suppressed, whereby an amount of generated heat (0.37 kW) is obtained. In addition, the amount of absorbed heat (0.55 kW) during electric power generation by the second fuel cell 3A, becomes approximately equal to the amount of absorbed heat (0.58 kW) during electric power generation by the fuel cell on the first stage in the comparative example due to internal reforming of the methane whose reaction is suppressed in the first fuel cell 1A. However, in the second fuel cell 3A, the amount of generated heat (1.18 kW) exceeds the amount of absorbed heat (0.55 kW) due to its large electric power generation capacity and therefore it is possible to secure the temperature required for stable operation.

    [0039] In the present embodiment, it is possible to suppress the amount of generated heat by injected fuel to be low and obtain an approximately equal amount of generated electric power. Since, in the comparative example of Fig. 5, the amount of generated electric power (slant line part) is 3.16 (0.76+2.4) kW against the amount of heat 6.45 (5.05+1.4) kW by injected fuel, the electric power generation efficiency turns out to be 48%. The present embodiment, in contrast, exhibits a higher efficiency of 62% because the amount of generated electric power (slant line part) is 3.11 (0.75+2.36) kW against the amount of heat 5.03 kW by injected fuel.

    [0040] Fig. 6 illustrates a methane reaction suppressing function of a second embodiment. Fig. 6(a) illustrates a schematic cross-sectional view of an electrolyte 47B and fuel poles 49B of a first fuel cell 1B on the first stage, and Fig. 6(b) illustrates a schematic cross-sectional view of an electrolyte 51B and fuel poles 53B of a second fuel cell 3B on the second stage.

    [0041] In the second embodiment, the fuel poles 49B of the first fuel cell 1B on the first stage includes Ni (nickel) and BCZY (BaCeZrY) which is a proton conductive material. The fuel poles 53B of the second fuel cell 3B on the second stage includes Ni and YSZ, similarly to the first embodiment. The electrolytes 47B and 51B are formed with a material including YSZ, similarly to the first embodiment.

    [0042] Using a proton conductive material as the material of the fuel poles 49B allows for selective use of hydrogen during electric power generation in comparison with methane or carbon monoxide, whereby reaction of methane can be suppressed. In other words, the second embodiment is intended to provide the first fuel cell 1B on the first stage with a methane reaction suppressing function by using BCZY which is a proton conductive material as the material of the fuel poles 49B. Accordingly, the first fuel cell 1B can suppress the amount of absorbed heat during steam reforming reaction (endothermic reaction), even when a large amount of methane is included in the fuel reformed by the reformer 19.

    [0043] Therefore, similarly to the first embodiment, the first fuel cell 1B can cause the amount of generated heat to exceed the amount of absorbed heat, thereby securing the temperature required for stable operation. As a result, it is possible to suppress decrease of the electric power generation efficiency in the fuel cell system.

    [0044] In this case, it becomes unnecessary to introduce a more-than-required amount of air into raw fuel to reduce methane during reforming, or heat the air for electric power generation beyond the operating temperature of the first fuel cell 1B, in order to appropriately maintain the temperature of the first fuel cell 1B on the first stage. As a result, it is possible to suppress decrease of the electric power generation efficiency of the fuel cell system.

    [0045] Fig. 7 illustrates a methane reaction suppressing function of a third embodiment. Fig. 7(a) illustrates a schematic cross-sectional view of an electrolyte 47C and fuel poles 49C of a first fuel cell 1C on the first stage, and Fig. 7(b) illustrates a schematic cross-sectional view of an electrolyte 51C and fuel poles 53C of a second fuel cell 3C on the second stage.

    [0046] In the third embodiment, the electrolyte 47C of the first fuel cell 1C on the first stage includes BCZY which is a proton conductive material. The electrolyte 51C of the second fuel cell 3C on the second stage includes YSZ, similarly to the first embodiment. The fuel poles 49C and 53C include Ni and YSZ, similarly to the first embodiment.

    [0047] Using a proton conductive material as the material of the electrolyte 47C allows for selective use of hydrogen during electric power generation in comparison with methane and carbon monoxide, whereby reaction of methane can be suppressed. In other words, the third embodiment is intended to provide the first fuel cell 1C on the first stage with a methane reaction suppressing function by using BCZY which is a proton conductive material as the material of the electrolyte 47C. Accordingly, the first fuel cell 1C can suppress the amount of absorbed heat during steam reforming reaction (endothermic reaction), even when a large amount of methane is included in the reformed fuel by the reformer 19.

    [0048] Therefore, similarly to the first embodiment, the first fuel cell 1C can cause the amount of generated heat to exceed the amount of absorbed heat, thereby securing the temperature required for stable operation. As a result, it is possible to suppress decrease of the electric power generation efficiency in the fuel cell system.

    [0049] In this case, it becomes unnecessary to introduce a more-than-required amount of air into raw fuel to reduce methane during reforming, or heat the air for electric power generation beyond the operating temperature of the first fuel cell 1C, in order to appropriately maintain the temperature of the first fuel cell 1C on the first stage. As a result, it is possible to suppress decrease of the electric power generation efficiency of the fuel cell system.

    [0050] Fig. 8 illustrates a methane reaction suppressing function of a fourth embodiment. The fourth embodiment, which is a modified example of the first embodiment illustrated in Fig. 3, has N fuel cells piping-connected in series, N being three or more, in addition to a first fuel cell 1D on the first stage and the second fuel cell 3D on the second stage. The fuel cell on the (N-1)-th stage is referred to as the (N-1)-th fuel cell 55D, and the fuel cell on the N-th stage is referred to as the N-th fuel cell 57D. Note that, in Fig. 8, only the fuel supply piping 11 in Fig. 11 is illustrated as the connection piping, whereas the air supply piping is omitted.

    [0051] Each fuel pole of the plurality of fuel cells 1D to 57D includes Ni and YSZ, similarly to the first embodiment of Fig. 3. Each electrolyte also includes YCZ, similarly to the first embodiment. Similarly to the first embodiment, the thickness T1 of the fuel poles of the first fuel cell 1D on the first stage is made thinner than the thickness T2 of the fuel poles of the second fuel cell 3D on the second stage.

    [0052] The thickness of the fuel poles is made thinnest at the first fuel cell 1D on the first stage and thickest at the N-th fuel cell 57D on the N-th stage which is the last stage, with the thickness gradually becoming thicker from the first fuel cell 1D to the N-th fuel cell 57D. In other words, letting TN-1 be the thickness of the fuel poles of the (N-1)-th fuel cell 55D and TN be the thickness of the fuel poles of the N-th fuel cell 57D, T1 <T2 <····< TN-1 <TN holds.

    [0053] As described in the first embodiment of Fig. 3, thinning the thickness of the fuel poles results in suppressing methane reaction. Accordingly, when a plurality of fuel cells is connected in series, making the thickness of the fuel poles on later stages thicker results in weakening the function of suppressing methane reaction in later stages.

    [0054] In other words, the fourth embodiment is intended to provide the plurality of fuel cells on the second and later stages with a later-stage methane reaction suppressing function, so that the function of suppressing methane reaction to be exhibited by the later-stage methane reaction suppressing function is gradually weakened at later stages.

    [0055] Methane whose reaction is suppressed in a fuel cell on an upper stage flows into a fuel cell on a lower stage, and therefore there may be assumed a case where an uneven temperature distribution occurs inside the fuel cell on the lower stage, or, depending on the amount of generated electric power, the amount of endothermic reaction exceeds the amount of generated heat. Accordingly, measures are taken to suppress the amount of endothermic reaction of methane by weakening the methane reaction suppressing function in fuel cells on later stages so that the temperature distribution inside the fuel cell becomes more even, or the amount of absorbed heat does not exceed the amount of generated heat by electric power generation.

    [0056] Fig. 9 illustrates a methane reaction suppressing function of a fifth embodiment. The fifth embodiment is a combination of the ideas of the third embodiment illustrated in Fig. 7 and the fourth embodiment illustrated in Fig. 8. The fifth embodiment, similarly to Fig. 8, has N fuel cells piping-connected in series, N being three or more, in addition to a first fuel cell 1E on the first stage and a second fuel cell 3E on the second stage. A fuel cell on the (N-1) is referred to as the (N-1)-th fuel cell 55E, and the fuel cell on the N-th stage is referred to as the N-th fuel cell 57E. Note that, in Fig. 9, only the fuel supply piping 11 in Fig. 11 is illustrated as the connection piping, whereas the air supply piping is omitted.

    [0057] In the fifth embodiment, respective electrolytes of the first fuel cell 1E to the (N-1)-th fuel cell 55E, except for the N-th fuel cell 57E on the last stage, include BCZY, which is a proton conductive material similarly to the electrolyte 47C of the first fuel cell 1C in Fig. 7. In addition, respective electrolytes of the second fuel cell 3E on the second stage to the N-th fuel cell 57E on the last stage, except for the first fuel cell 1E on the first stage, include YCZ, which is an oxide conductive material. Each fuel pole of the fuel cells 1E to 57E includes Ni and YSZ, similarly to Fig. 7.

    [0058] The electrolyte of the first fuel cell 1E on the first stage does not include YCZ, and therefore, letting P:Q be the ratio between the proton conductive material and the oxide conductive material, a ratio of P:Q=1:0 is obtained. The electrolyte of the N-th fuel cell 57E on the last stage does not include BCZY, and therefore a ratio of P:Q=0:1 is obtained. Subsequently, the electrolyte of the second fuel cell 3E on the second stage exhibits a ratio of P:Q =0.9: 0.1, and the electrolyte of the (N-1)-th fuel cell 55E exhibits a ratio of P:Q =0.1:0.9.

    [0059] As thus described, the composition ratio between the proton conductive material and the oxide conductive material is set for respective electrolytes of the first fuel cell 1E on the first stage to the N-th fuel cell 57E on the last stage so that the proportion of the proton conductive material in later stages becomes lower.

    [0060] As described in the third embodiment of Fig. 7, using a proton conductive material as the material of the electrolyte allows for selective use of hydrogen during electric power generation in comparison with methane or carbon monoxide, whereby reaction of methane can be suppressed. Therefore, reducing the proportion of the proton conductive material for fuel cells on later stages weakens the function of suppressing methane reaction for later stages, similarly to the fourth embodiment of Fig. 8.

    [0061] In other words, the fifth embodiment, similarly to the fourth embodiment, is intended to provide the plurality of fuel cells on the second and later stages with a later-stage methane reaction suppressing function, so that the function of suppressing methane reaction to be exhibited by the later-stage methane reaction suppressing function is gradually weakened for later stages. Therefore, the fifth embodiment brings about an operational effect that is similar to the fourth embodiment.

    [0062] Fig. 10 illustrates a methane reaction suppressing function of a sixth embodiment. The sixth embodiment, similarly to the fourth embodiment of Fig. 8 and the fifth embodiment of Fig. 9, has a plurality of fuel cells ranging from a first fuel cell 1F to the N-th fuel cell 57F piping-connected in series. The sixth embodiment has a discharged fuel reformer 59 between fuel cells which are adjacent to each other among a plurality of fuel cells. Each discharged fuel reformer 59 reforms discharged fuel discharged from a fuel cell on a preceding stage (upstream).

    [0063] The fuel cell of the preceding stage has a thermodynamic non-equilibrium composition in which a large amount of reaction-suppressed methane exists and also the content ratio of water and carbon dioxide is high due to electric power generation. Therefore, the composition is reformed to thermodynamic equilibrium by providing the discharged fuel reformer 59 on the fuel supply piping 11 between fuel cells.

    [0064] During reforming, steam reforming reaction (endothermic reaction) of methane occurs, and although the temperature of reformed fuel becomes lower than the temperature of surrounding fuel cells, heat exchange with the fuel supply piping 11 which has reached a high temperature causes the temperature of reformed fuel to rise. Rising of the reformed fuel temperature prevents the temperature distribution in fuel cells on later stages from becoming uneven, or the amount of absorbed heat from exceeding the amount of generated heat by electric power generation.

    [0065] Fig. 11 illustrates a seventh embodiment of the present invention. The seventh embodiment has a discharged fuel circulation mechanism 61 added to the first embodiment of Fig. 1 for supplying, in a circulating manner, the reformer 19 with a part of discharged fuel containing water discharged from the second fuel cell 3 on the second stage located at the furthermost stage. The rest of the configuration is similar to that of Fig. 1.

    [0066] The discharged fuel circulation mechanism 61 has a fuel circulation blower 63 provided on the fuel discharge pipe 23, and a fuel circulation piping 65 for connecting the fuel circulation blower 63 and the reformer 19. The fuel circulation blower 63 is supposed to divide the discharged fuel containing water discharged from the second fuel cell 3 and send the divided discharged fuel toward both the reformer 19 and the combustor 21.

    [0067] When reforming fuel, a higher reforming efficiency is obtained by steam reforming (endothermic reaction) of fuel and water than by partial oxidation reforming (exothermic reaction) of fuel and oxygen. Therefore, water generated in fuel gas due to electric power generation is supplied to the reformer 19 in a circulating manner to perform steam reforming. Accordingly, the reforming efficiency increases, and the portion of fuel used in the system also increases.

    [0068] The raw fuel used in the respective embodiments described above is hydrocarbon-based or alcohol-based liquid fuel. In particular, for use in a mobile body such as an automobile, liquid fuel with a high energy density is suitable, among which hydrocarbon-based fuel such as gasoline, light oil and kerosene, or alcohol-based fuel such as methanol and ethanol is easily available with increased convenience.

    [0069] The aforementioned alcohol-based fuel may contain water. In the case of alcohol fuel containing water, a relatively low combustion gas temperature suffices for the combustor 21 to warm the raw fuel before reforming, and therefore the fuel temperature after heating does not become very high. Accordingly, alcohol fuel containing water will have a low reformed fuel temperature after reforming, and a high concentration of methane in the reformed fuel. Therefore, alcohol fuel containing water turns out to be suitable for a multi-stage fuel cell system having a methane reaction suppressing function.

    [0070]  In addition, it is not necessary to use the discharged fuel circulation mechanism 61 which has been used in the seventh embodiment of Fig. 11 to supply water to the reformer 19 for reforming fuel by the reformer 19, whereby the system configuration may be simplified in comparison with the seventh embodiment when performing steam reforming (endothermic reaction).

    [0071] Although the present invention has been described above by reference to the embodiments, the present invention is not limited to those, and it will be apparent to these skilled in the art that various modifications and improvements can be made.

    [0072] For example, the configuration with the thickness of the fuel poles 49A of the first fuel cell 1A in Fig. 3 being thinned, the configuration with the fuel poles 49B of the first fuel cell 1B in Fig. 6 including a proton conductive material, and the configuration with the electrolyte 47C of the first fuel cell 1C in Fig. 7 including a proton conductive material may be combined as appropriate. In addition, the respective embodiments of Figs. 8, 9, and 10 can be combined as appropriate.

    INDUSTRIAL APPLICABILITY



    [0073] The present invention is applied to a fuel cell system having a plurality of fuel cells connected in series.

    REFERENCE SIGNS LIST



    [0074] 

    1, 1A, 1B, 1C, 1D, 1E, 1F first fuel cell (fuel cell on first stage)

    3, 3A, 3B, 3C, 3D, 3E, 3F second fuel cell (fuel cell on second stage)

    19 reformer

    59 discharged fuel reformer

    61 discharged fuel circulation mechanism




    Claims

    1. A fuel cell system comprising:

    the plurality of fuel cells (1,3; 1A,3A; 1B.3B; 1C,3C; 1D,3D,55D,57D; 1E,3E,55E,57E; 1F,3F,55F,57F) connected to each other in series; and

    a reformer (19) configured to reform raw fuel, wherein

    reformed fuel by the reformer (19) is supplied to a first stage of the plurality of fuel cells (1; 1A; 1B; 1C; 1D; 1E; 1F), and

    the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) is located upstream of the fuel cell on a second stage (3; 3A; 3B; 3C; 3D; 3E; 3F) in the flow of fuel and air,

    characterized in that

    the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) is configured to have a reaction of methane in the reformed fuel that is more suppressed, thereby suppressing an amount of absorbed heat relative to an amount of generated heat in the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F), than in at least one fuel cell on the second and later stages (3; 3A; 3B; 3C; 3D,55D,57D; 3E,55E,57E; 3F,57F), and

    the suppression of the reaction of methane in the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) is provided by one or more of:

    the thickness of fuel poles forming a three-phase interface in the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) thinner than that of at least one fuel cell on the second and later stages (3; 3A; 3B; 3C; 3D,55D,57D; 3E,55E,57E; 3F,57F); and

    using a proton conductive material as a material of fuel poles.


     
    2. The fuel cell system according to claim 1, wherein
    the suppression of the reaction of methane in the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) is further provided by using a proton conductive material as a material of electrolyte.
     
    3. The fuel cell system according to claim 1 or 2, wherein
    the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F) has an electrode with a smaller area in which fuel and oxidizer react than that of at least one fuel cell on the second and later stages (3; 3A; 3B; 3C; 3D,55D,57D; 3E,55E,57E; 3F,57F).
     
    4. The fuel cell system according to any of claims 1 to 3, wherein
    at least one fuel cell on the second and later stages (3; 3A; 3B; 3C; 3D,55D; 3E,55E; 3F,57F) is configured to have a reaction of methane in the reformed fuel suppressed, thereby suppressing an amount of absorbed heat relative to an amount generated heat in the at least one fuel cell on the second and later stages (3; 3A; 3B; 3C; 3D,55D; 3E,55E; 3F,57F), by an amount less than that of the fuel cell on the first stage (1; 1A; 1B; 1C; 1D; 1E; 1F).
     
    5. The fuel cell system according to claim 4, wherein
    with regard to a plurality of fuel cells on the second and later stages (3; 3A; 3B; 3C; 3D,55D; 3E,55E; 3F,57F), the later-stage, the less the amount of suppression of the reaction of methane.
     
    6. The fuel cell system according to any one of claims 1 to 5, wherein
    a discharged fuel reformer (59) configured to reform discharged fuel discharged from a fuel cell of a preceding stage is provided between each pair of the plurality of fuel cells.
     
    7. The fuel cell system according to any one of claims 1 to 6, wherein
    the raw fuel is hydrocarbon-based or alcohol-based liquid fuel.
     
    8. The fuel cell system according to any one of claims 1 to 7, further comprising
    a discharged fuel circulation mechanism (61) for supplying, in a circulating manner, the reformer (19) with fuel containing water discharged from a fuel cell located on the last stage of the plurality of fuel cells.
     
    9. The fuel cell system according to claim 8, wherein
    the alcohol-based liquid fuel contains water.
     


    Ansprüche

    1. Brennstoffzellen-System, das umfasst:

    die Vielzahl von Brennstoffzellen (1, 3; 1A, 3A; 1B, 3B; 1C, 3C; 1D, 3D, 55D, 57D; 1E, 3E, 55E, 57E; 1F, 3F, 55F, 57F), die in Reihe miteinander verbunden sind; und

    einen Reformer (19), der zum Reformieren von Roh-Brennstoff ausgeführt ist, wobei

    durch den Reformer (19) reformierter Brennstoff einer ersten Stufe der Vielzahl von Brennstoffzellen (1; 1A; 1B; 1C; 1D; 1E; 1F) zugeführt wird, und

    die Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) in dem Strom von Brennstoff und Luft stromauf von der Brennstoffzelle einer zweiten Stufe (3; 3A; 3B; 3C; 3D; 3E; 3F) positioniert ist,

    dadurch gekennzeichnet, dass

    die Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) so ausgeführt ist, dass eine Reaktion von Methan in dem reformierten Brennstoff stärker beschränkt und dadurch eine Menge absorbierter Wärme relativ zu einer Menge erzeugter Wärme in der Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) beschränkt wird, als in wenigstens einer Brennstoffzelle der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D, 57D; 3E, 55E, 57E; 3F, 57F), und

    die Beschränkung der Reaktion von Methan in der Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) dadurch ermöglicht wird, dass

    die Dicke von Brennstoff-Polen, die eine Dreiphasen-Grenzfläche in der Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) bilden, dünner sind als die wenigstens einer Brennstoffzelle der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D, 57D; 3E, 55E, 57E; 3F, 57F); oder/und

    ein protonenleitendes Material als ein Material von Brennstoff-Polen eingesetzt wird.


     
    2. Brennstoffzellen-System nach Anspruch 1, wobei
    die Beschränkung der Reaktion von Methan in der Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) des Weiteren dadurch ermöglicht wird, dass ein protonenleitendes Material als ein Elektrolytmaterial eingesetzt wird.
     
    3. Brennstoffzellensystem nach Anspruch 1 oder 2, wobei
    die Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) eine Elektrode mit einer kleineren Fläche, an der Brennstoff und Oxidans reagieren, als der wenigstens einer Brennstoffzelle der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D, 57D; 3E, 55E, 57E; 3F, 57F) hat.
     
    4. Brennstoffzellensystem nach einem der Ansprüche 1 bis 3, wobei
    wenigstens eine Brennstoffzelle der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D; 3E, 55E; 3F, 57F) so ausgeführt ist, dass eine Reaktion von Methan in dem reformierten Brennstoff in einem Maß beschränkt und dadurch eine Menge absorbierter Wärme relativ zu einer Menge erzeugter Wärme in der wenigstens einen Brennstoffzelle der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D; 3E, 55E; 3F, 57F) in einem geringeren Maß als dem der Brennstoffzelle der ersten Stufe (1; 1A; 1B; 1C; 1D; 1E; 1F) beschränkt wird.
     
    5. Brennstoffzellen-System nach Anspruch 4, wobei
    bei einer Vielzahl von Brennstoffzellen der zweiten und späterer Stufen (3; 3A; 3B; 3C; 3D, 55D; 3E, 55E; 3F, 57F) das Maß an Beschränkung der Reaktion von Methan umso geringer ist, je später die Stufe ist.
     
    6. Brennstoffzellen-System nach einem der Ansprüche 1 bis 5, wobei
    ein Reformer (59) für abgeleiteten Brennstoff, der so ausgeführt ist, dass er abgeleiteten Brennstoff reformiert, der aus einer Brennstoffzelle einer vorangehenden Stufe abgeleitet wird, zwischen jedem Paar der Vielzahl von Brennstoffzellen vorhanden ist.
     
    7. Brennstoffzellen-System nach einem der Ansprüche 1 bis 6, wobei
    der Roh-Brennstoff flüssiger Brennstoff auf Kohlenwasserstoff- Basis oder Alkohol-Basis ist.
     
    8. Brennstoffzellen-System nach einem der Ansprüche 1 bis 7, das des Weiteren umfasst:
    einen Zirkulations-Mechanismus (61) für abgeleiteten Brennstoff, mit dem dem Reformer (19) zirkulierend Wasser enthaltender Brennstoff zugeführt wird, der aus einer Brennstoffzelle abgeleitet wird, die sich auf der letzten Stufe der Vielzahl von Brennstoffzellen befindet.
     
    9. Brennstoffzellen-System nach Anspruch 8, wobei
    der flüssige Brennstoff auf Alkohol-Basis Wasser enthält.
     


    Revendications

    1. Système de piles à combustible comprenant :

    la pluralité de piles à combustible (1, 3 ; 1A, 3A ; 1B, 3B ; 1C, 3C ; 1D, 3D, 55D, 57D ; 1E, 3E, 55E, 57E ; 1F, 3F, 55F, 57F) connectées les unes aux autres en série ; et

    un reformeur (19) configuré pour reformer le combustible brut, dans lequel du combustible reformé par le reformeur (19) est délivré dans un premier étage de la pluralité de piles à combustible (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F), et

    la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) est située en amont de la pile à combustible sur un second étage (3 ; 3A ; 3B ; 3C ; 3D ; 3E ; 3F) dans l'écoulement de combustible et d'air,

    caractérisé en ce que

    la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) est configurée pour avoir une réaction de méthane dans le combustible reformé qui est plus atténuée, en atténuant ainsi une quantité de chaleur absorbée par rapport à une quantité de chaleur générée dans la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F), que dans au moins une pile à combustible sur le second étage et des étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D, 57D ; 3E, 55E, 57E ; 3F, 57F), et

    l'atténuation de la réaction de méthane dans la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) est assurée par une ou plusieurs parmi :

    l'épaisseur de pôles de combustible formant une interface triphasée dans la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) plus mince que celle d'au moins une pile à combustible sur le second étage et étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D, 57D ; 3E, 55E, 57E ; 3F, 57F) ; et

    l'utilisation d'un matériau conducteur de protons comme matériau de pôles de combustible.


     
    2. Système de piles à combustible selon la revendication 1, dans lequel
    l'atténuation de la réaction de méthane dans la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) est en outre assurée en utilisant un matériau conducteur de protons comme matériau d'électrolyte.
     
    3. Système de piles à combustible selon la revendication 1 ou 2, dans lequel
    la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F) a une électrode avec une surface plus petite dans laquelle le combustible et l'oxydant réagissent par rapport à celle d'au moins une pile à combustible sur le second étage et étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D, 57D ; 3E, 55E, 57E ; 3F, 57F).
     
    4. Système de piles à combustible selon l'une quelconque des revendications 1 à 3, dans lequel
    au moins une pile à combustible sur le second étage et étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D ; 3E, 55E ; 3F, 57F) est configurée pour avoir une réaction de méthane dans le combustible reformé atténuée, en atténuant ainsi une quantité de chaleur absorbée par rapport à une quantité de chaleur générée dans la au moins une pile à combustible sur le second étage et étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D ; 3E, 55E ; 3F, 57F), d'une quantité inférieure à celle de la pile à combustible sur le premier étage (1 ; 1A ; 1B ; 1C ; 1D ; 1E ; 1F).
     
    5. Système de piles à combustible selon la revendication 4, dans lequel
    en ce qui concerne une pluralité de piles à combustible sur le second étage et étages ultérieurs (3 ; 3A ; 3B ; 3C ; 3D, 55D ; 3E, 55E ; 3F, 57F), plus le stade est postérieur, moins la quantité d'atténuation de la réaction de méthane est importante.
     
    6. Système de piles à combustible selon l'une quelconque des revendications 1 à 5, dans lequel
    un reformeur de combustible déchargé (59) configuré pour reformer du combustible déchargé qui est déchargé d'une pile à combustible d'un étage précédent est agencé entre chaque paire de la pluralité de piles à combustible.
     
    7. Système de piles à combustible selon l'une quelconque des revendications 1 à 6, dans lequel
    le combustible brut est un combustible liquide à base d'hydrocarbures ou à base d'alcool.
     
    8. Système de piles à combustible selon l'une quelconque des revendications 1 à 7, comprenant en outre
    un mécanisme de circulation de combustible déchargé (61) pour alimenter, d'une manière circulante, le reformeur (19) en combustible contenant de l'eau déchargé d'une pile à combustible située sur le dernier étage de la pluralité de piles à combustible.
     
    9. Système de piles à combustible selon la revendication 8, dans lequel le combustible liquide à base d'alcool contient de l'eau.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description