WO2013180299A1 - セルおよびセルスタック装置並びに電気化学モジュール、電気化学装置 - Google Patents
セルおよびセルスタック装置並びに電気化学モジュール、電気化学装置 Download PDFInfo
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- WO2013180299A1 WO2013180299A1 PCT/JP2013/065296 JP2013065296W WO2013180299A1 WO 2013180299 A1 WO2013180299 A1 WO 2013180299A1 JP 2013065296 W JP2013065296 W JP 2013065296W WO 2013180299 A1 WO2013180299 A1 WO 2013180299A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a cell stack device in which a plurality of cells are electrically connected via a current collecting member and a cell such as a fuel battery cell, and an electrochemical module, electrochemical device in which the cell stack device is stored in a storage container
- the present invention relates to an electrochemical device including a module.
- a fuel cell (hereinafter also referred to as a cell) has a structure in which a solid electrolyte layer is sandwiched between a fuel electrode layer and an oxygen electrode layer. The cell generates power by flowing fuel gas through the fuel electrode layer and oxygen-containing gas through the oxygen electrode layer and heating the cell to 1000 to 1050 ° C. (see, for example, Patent Document 1).
- Patent Document 2 the reaction loss of the oxygen electrode layer is increased by adjusting the specific surface area of the particles constituting the oxygen electrode layer to 1.5 to 9.0 m 2 / g and the pore diameter to 30 to 100 nm. It is disclosed that it is possible to suppress the decrease in the output of the cell after being used for a long time.
- An object of the present invention is to provide a cell, a cell stack, an electrochemical module, and an electrochemical device that can suppress a decrease in output.
- the cell of the present invention has a fuel electrode layer disposed on one side of a solid oxide electrolyte layer and an oxygen electrode layer disposed on the other side, the oxygen electrode layer having a plurality of pores, and the oxygen electrode layer 3 has three or more peaks in the pore diameter distribution of the pores observed in an arbitrary cross section.
- the cell stack device of the present invention is formed by electrically connecting a plurality of the cells via a current collecting member, and the electrochemical module of the present invention includes the cell stack in a storage container.
- the electrochemical device of the present invention comprises the above-described electrochemical module.
- the oxygen electrode layer has a plurality of pores, and has three or more peaks in the pore diameter distribution of the pores observed in an arbitrary cross section, for example, constituting the first peak.
- the effect of efficiently taking in air at the time of power generation is the effect of taking pores with a small pore size, and the effect of suppressing the pores from decreasing due to deterioration over time even when the pores with an intermediate pore size constituting the second peak are used for a long period of time.
- the pores having a large pore diameter constituting the third peak exhibit an effect of adjusting the porosity of the oxygen electrode layer to perform efficient power generation, and can suppress a decrease in output over a long period of time.
- an electrochemical module, and an electrochemical device using such a cell output reduction can be suppressed.
- the structure of the cell of this embodiment is shown, (a) Cross section, (b) The side view seen from the interconnector layer side.
- (A) It is a cross-sectional photograph about an example of the oxygen electrode layer used for the cell of FIG. 1, (b) It is a figure for demonstrating the method of calculating
- 2 shows the pore size distribution of the oxygen electrode layer of FIG. 2, (a) For each pore, two pore sizes estimated by photographs of two different magnifications of a scanning electron microscope (SEM) during the calculation of the pore size distribution.
- SEM scanning electron microscope
- FIG. 2 shows a structure of a cell stack apparatus including the cell of FIG. 1, (a) a side view, and (b) a transverse sectional view of a broken line part of (a).
- FIG. 2 shows an external appearance perspective view which shows an example of the electrochemical module which comprises the cell stack apparatus of FIG. 4, and shows the state before storing a cell stack apparatus in a storage container.
- FIG. 1A and 1B show an example of a solid oxide cell 1 according to the present embodiment.
- FIG. 1A is a cross-sectional view thereof
- FIG. 1B is a side view of the cell 1 viewed from the interconnector layer side of FIG. is there.
- a part of each component of the cell 1 is shown in an enlarged manner.
- This cell 1 is a so-called hollow plate type fuel cell, an elliptical shape with a flat cross section, and a porous conductive support body (hereinafter simply referred to as a support body) having an elliptical column shape as a whole. ) 2. That is, the support 2 has a pair of flat surfaces n parallel to each other and a pair of arcuate surfaces (side surfaces) m respectively connecting the pair of flat surfaces n, as understood from the shape shown in FIG. The pair of flat surfaces n are substantially parallel to each other.
- a plurality of fuel gas passages 3 are provided in the support 2 so as to penetrate in the longitudinal direction L at appropriate intervals. Further, the cell 1 has a structure provided so that various members described later surround the outer periphery of the support 2.
- the support 2 has a porous fuel electrode layer 8 disposed so as to cover one flat surface n (the lower surface in FIG. 1) and the arcuate surfaces m on both sides.
- a solid oxide electrolyte layer 9 is disposed so as to cover the fuel electrode layer 8.
- a porous oxygen electrode layer is provided at a position along the flat surface n outside the electrolyte layer 9 (the lower surface in FIG. 1A) so as to face the fuel electrode layer 8 through the intermediate layer 12. 10 is arranged.
- the fuel electrode layer 8 is disposed on one main surface of the electrolyte layer 9, the oxygen electrode layer 10 is disposed on the other main surface, and the electrolyte layer 9 is sandwiched between the fuel electrode layer 8 and the oxygen electrode layer 10. It is.
- the intermediate layer 12 has a strong bonding between the electrolyte layer 9 and the oxygen electrode layer 10 and a reaction layer having a high electrical resistance is formed by a reaction between the component of the electrolyte layer 9 and the component of the oxygen electrode layer 10. It is provided for the purpose of suppressing.
- the difference in thermal expansion coefficient between the interconnector layer 11 and the support 2 is reduced.
- the interconnector layer 11 is disposed through an adhesion layer (not shown) provided for the purpose. That is, the fuel electrode layer 8 and the electrolyte layer 9 extend from one flat surface (the lower surface in FIG. 1A) to a part of the other flat surface n (the upper surface) via the arcuate surfaces m at both ends. In addition, both end portions of the interconnector layer 11 are laminated and joined to both end portions of the electrolyte layer 9.
- the support body 2 is surrounded by the electrolyte layer 9 and the interconnector layer 11, and the fuel gas flowing through the inside does not leak to the outside.
- the fuel gas supplied to the fuel electrode layer 8 and the oxygen-containing gas supplied to the oxygen electrode layer 10 are cut off with the electrolyte layer 9 as a boundary.
- the interconnector layer 11 having a rectangular planar shape is arranged so as to cover the upper end to the lower end in the longitudinal direction L of the support 2.
- the left and right side end portions are joined so as to overlap the surfaces of both end portions of the electrolyte layer 9.
- the portion where the fuel electrode layer 8 and the oxygen electrode layer 10 face each other through the electrolyte layer 9 functions as an electrode to generate power.
- an oxygen-containing gas such as air is allowed to flow outside the oxygen electrode layer 10
- a fuel gas hydrogen-containing gas
- the fuel electrode layer 8 is heated to a predetermined operating temperature to generate electricity.
- the current generated by the power generation is collected at the interconnector layer 11.
- the oxygen electrode layer 10 of this embodiment is made of a conductive ceramic made of a so-called ABO 3 type perovskite oxide.
- ABO 3 type perovskite oxide As the perovskite oxide, at least one of La-containing transition metal perovskite oxide, particularly LaMnO 3 oxide, LaFeO 3 oxide, and LaCoO 3 oxide in which Sr coexists in the A site is included. LaCoO 3 oxides are preferable because they have high electrical conductivity at an operating temperature of about 600 to 1000 ° C. In this perovskite oxide, Fe or Mn may be dissolved in the B site together with Co.
- the oxygen electrode layer 10 needs to have gas permeability.
- the oxygen electrode layer 10 has an open porosity of 20% or more, particularly 30 to 50%.
- the thickness of the oxygen electrode layer 10 is preferably 30 to 100 ⁇ m from the viewpoint of current collection.
- the oxygen electrode layer 10 has a large number of pores, and the pore diameter distribution of FIG.
- the first peak p1, the second peak p2, and the third peak p3 are provided in the order of decreasing pore diameter.
- each peak in the present invention does not indicate only the maximum value of the peak, which is the maximum value of each peak, but indicates the entire peak including the skirt extending on both sides around the maximum value of each peak.
- the pores constituting the first peak p1, the second peak p2, and the third peak p3 are defined as the first pore 20, the second pore 21, and the third pore 22, respectively.
- the number of peaks is not limited to three, and may have four or more peaks. In the following description, a case where three peaks are provided will be described as an example.
- the pores 20 constituting the first peak p1 have a high effect of increasing the content of air contained in the oxygen electrode layer 10, and have the effect of efficiently taking in air when the cell 1 is used and exhibiting high power generation efficiency. Have.
- the first pores 20 in the oxygen electrode layer 10 tend to gradually disappear due to the operation of the cell 1, but the particles constituting the oxygen electrode layer 10 due to the presence of the second pores 21 constituting the second peak p2. Therefore, the rate at which the first pores 20 in the oxygen electrode layer 10 disappear can be reduced. As a result, even if the cell 1 is used for a long time, the amount of air flowing in the oxygen electrode layer 10 is prevented from decreasing due to deterioration over time, and the effect of suppressing deterioration over time in power generation efficiency is obtained.
- the third pores 22 constituting the third peak p3 adjust the porosity of the oxygen electrode layer 10 to optimize the amount of air flowing through the oxygen electrode layer 10, and as a result, perform efficient power generation. It has the effect of exhibiting high power generation efficiency. That is, when the pore distribution constituting the oxygen electrode layer 10 has three or more peaks, the oxygen electrode layer 10 has high power generation performance, and this high power generation performance is unlikely to deteriorate over a long period of time.
- the structure of the oxygen electrode layer 10 is observed with a scanning electron microscope (SEM) at a magnification of 500 to 1000 times. 2 is observed), and the pore size distribution (Dl in FIG. 3A) in the low magnification observation is obtained from the size and the number of the pores.
- SEM scanning electron microscope
- the magnification of SEM is increased to 1500 to 5000 times, and the pore size distribution in high magnification observation from the size and number of pores in one visual field (mainly the first pore 20 is observed) (FIG. 3 (a)). Ds).
- the second pore 21 may be observed in the high magnification observation.
- the total pore size distribution of the oxygen electrode layer 10 (Dt in FIG. 3A) is obtained by combining these three pore size distributions.
- the magnification corresponding to the ratio of the area of the pore size distribution (Dl) in the low magnification observation to the area of the pore size distribution (Ds) in the high magnification observation is multiplied by the number of each pore size distribution.
- Dl and Ds are added together to obtain Dt.
- the equivalent circle diameter which is the diameter when the shape of each pore is converted into a circle by image analysis or the like, is expressed as the pore diameter.
- each peak has a normal distribution in this entire pore size distribution (Dt)
- the pore distribution of each peak corrected by peak separation is derived as shown in FIG. Can do.
- observation at each magnification is observed at five arbitrary positions at each magnification, and the maximum value and number ratio of each peak are calculated from the average value of the measurement results.
- the first peak p1 maximum value p1t has a pore diameter of 0.02 to 1 ⁇ m
- the second peak p2 has a maximum value p2t of 1 to 5 ⁇ m
- the third peak When the maximum value p3t of p3 is in the range of the pore diameter of 4 to 25 ⁇ m, the above effect is more remarkably exhibited.
- four or more peaks when four or more peaks exist, four or more peaks are classified into three of a 1st peak, a 2nd peak, and a 3rd peak by the position of the maximum value of those peaks.
- the first pores 20 are 80 to 90% in number ratio with respect to all the pores
- the second pores 21 are 9 to 19% in number ratio with respect to all the pores.
- 22 is present in a ratio of 0.3 to 2% in terms of the number ratio with respect to all pores.
- These values can be calculated by comparing the areas of the peaks p1, p2, and p3 (see FIG. 3B) obtained by separating the entire pore size distribution (Dt) by peak separation. That is, the area ratio of the first peak p1 is 80 to 90%, the area ratio of the second peak p2 is 9 to 19%, and the area ratio of the third peak p3 is 0.3 to 2%. The effect is exhibited more efficiently.
- the range of the pore diameter in which the maximum value p1t of the first peak p1 exists is the range of 0.15 to 0.6 ⁇ m among the 0.02 to 1 ⁇ m. If the maximum value p1t of the first peak p1 is within this range, the sinterability of the particles constituting the oxygen electrode layer 10 is low, and the shape of the particles constituting the oxygen electrode layer 10 even when the cell 1 is activated. Small change. Therefore, a part of the components contained in the oxygen electrode layer 10 diffuses by the operation of the cell 1 and moves to the intermediate layer 12 and the electrolyte layer 9 side, and between the intermediate layer 12 and the oxygen electrode layer 10, for example, Generation of high resistance compounds such as SrZrO 3 phase can be suppressed. As a result, it can suppress that the power generation efficiency of the cell 1 falls. Moreover, the specific surface area of the oxygen electrode layer 10 can be increased, the amount of oxygen supplied is high, and the power generation efficiency of the cell 1 is high.
- the pores in the range of the second peak p2 include flat pores having an aspect ratio of 3 to 10, particularly corresponding to the maximum value p2t of the second peak p2. It is desirable that the average aspect ratio of the second pores 21 having the pore diameter at the upper limit of the second peak p2 from the pore diameter is 3 to 10. Thereby, even if the cell 1 operates, the shape change of the particles constituting the oxygen electrode layer 10 can be reduced. Note that the average aspect ratio of the second pores 21 having the pore diameter corresponding to the maximum value p2t of the second peak p2 and the upper limit of the second peak p2 is the second aspect in the micrograph of the oxygen electrode layer 10.
- the second pore 21 having the upper limit pore diameter of the second peak p2 is specified from the pore diameter corresponding to the maximum value p2t of the peak p2, and the longest length of each second pore 21 is obtained.
- the width of the second pores 21 in the direction orthogonal to is measured.
- “the longest length of the second pores 21 / the width of the second pores 21” is measured as the aspect ratio of each second pore 21, and the average value is calculated as the average aspect ratio.
- the average aspect ratio of the first pores 20 having the pore diameter corresponding to the maximum value p1t of the first peak p1 to the lower limit of the first peak p1 is 1 to 3.
- the structure of the oxygen electrode layer 10 is composed of a porous portion 24, a dense portion 25, and a void portion 26.
- the porous part 24 is a part including many first pores 20 and has an effect of efficiently taking in air when the cell 1 is used and exhibiting high power generation efficiency.
- the dense part 25 is a part that hardly contains pores, and is a part that has a small shape change due to aging even when the cell 1 is used for a long period of time. Therefore, since the dense portion 25 suppresses deformation due to aging of the porous portion 24, it is possible to delay the disappearance of the first pores 20 in the porous portion 24 when the porous portion 24 contracts due to the operation of the cell 1. .
- the void portion 26 has an effect of adjusting the porosity of the entire oxygen electrode layer 10 to perform efficient power generation and exhibiting high power generation efficiency. As a result, the oxygen electrode layer 10 has high power generation performance, and the high power generation performance is unlikely to deteriorate over a long period of time.
- the porous part 24 is an area where a large number of first pores 20 exist.
- the second pores 21 exist inside the porous portion 24 or between the porous portion 24 and the dense portion 25.
- the dense portion 25 is a region where the first pores 20 are hardly present.
- the void portion 26 indicates a region where pores having a pore diameter of 10 ⁇ m or more exist.
- gap part 26 is determined as follows. First, pores having a pore diameter of 10 ⁇ m or more are specified as the void portion 26. Next, the oxygen electrode layer 10 is observed with an SEM at a magnification of 1500 to 3000 times to determine the boundary between the porous portion 24 and the dense portion 25.
- the boundary between the porous portion 24 and the dense portion 25 is three times the pore diameter at which the maximum value p1t of the peak of the first peak 20 with respect to each first pore 20 is present.
- a region surrounded by connecting the centers of the outermost circles (FIG. 2 ( A region surrounded by a white dotted line b) is defined as a porous portion 24.
- a region other than the porous portion 24 and the void portion 26 is defined as a dense portion 25.
- the dense portion 25 is formed so as to be surrounded by the porous portion 24 and the gap portion 26, and in the present embodiment, the dense portion 25 exists in a frame shape as a skeleton.
- the circle c protrudes from the end of the oxygen electrode layer 10 at the end of the oxygen electrode layer 10, the area of the pores is estimated except for the protruding portion.
- the outer peripheral length of the dense portion 25 is 10 times or more the pore diameter of the first pore 20, deformation of the dense portion 25 due to change with time can be further suppressed. Further, when the ratio of the square of the outer peripheral length of the dense portion 25 / the area of the dense portion 25 is 40 to 100 and the dense portion 25 has an elongated shape, the porosity in the oxygen electrode layer 10 can be optimized. At the same time, it is possible to further suppress a decrease in porosity due to a change with time. When there are a plurality of dense portions 25, the outer peripheral length is calculated using the average value of the outer peripheral lengths of the dense portions 25.
- the porous portion 24 is present in a ratio of 25 to 55 area%
- the dense portion 25 is present in a ratio of 15 to 35 area%
- the void portion 26 is present in a ratio of 10 to 60 area%. If it is this range, the said effect can be exhibited more efficiently.
- the intermediate layer 12 is provided between the oxygen electrode layer 10 and the electrolyte layer 9 for the purpose of preventing a reaction therebetween.
- it is made of a CeO 2 based sintered body containing a rare earth element other than Ce, for example, (CeO 2 ) 1-x (REO 1.5 ) x (wherein RE is Sm, It is at least one of Y, Yb, and Gd, and x has a composition represented by 0 ⁇ x ⁇ 0.3.
- Sm or Gd is used as RE from the viewpoint of reducing electric resistance, and it is made of, for example, CeO 2 in which 10 to 20 mol% of SmO 1.5 or GdO 1.5 is dissolved.
- the support 2 is required to be gas permeable in order to permeate the fuel gas up to the fuel electrode layer 8 and to be conductive in order to be connected to the interconnector layer 11 for current collection. Therefore, as the support 2, conductive ceramics, cermet, or the like can be used.
- the conductivity is preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.
- the open porosity is preferably 30% or more, particularly 35 to 50%.
- the support 2 is composed of an iron group metal component and an inorganic oxide such as Ni and / or Or it consists of NiO and a specific rare earth oxide.
- the specific rare earth oxide is used to make the thermal expansion coefficient of the support 2 close to the thermal expansion coefficient of the electrolyte layer 9, and is Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm.
- Rare earth oxides containing at least one element selected from the group consisting of Pr are used, and can be used in combination with Ni and / or NiO.
- rare earth oxides include Y 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Er 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Gd 2 O. 3 , Sm 2 O 3 , Pr 2 O 3 can be exemplified, there is almost no solid solution or reaction with Ni and / or NiO, and the thermal expansion coefficient is comparable to that of the electrolyte layer 9 and is inexpensive. terms is composed of at least one of Y 2 O 3 and Yb 2 O 3.
- Ni and / or NiO: rare earth oxide 35: 65 to 65 in that the good conductivity of the support 2 is maintained and the thermal expansion coefficient is approximated to that of the electrolyte layer 9. Is present in a volume ratio of 35.
- the support 2 may contain other metal components and oxide components as long as required characteristics are not impaired.
- the length of the flat surface n of the support 2 (the length of the support 2 in the width direction W) is 15 to 35 mm
- the length of the arc-shaped surface m (the length of the arc) is The thickness of the support 2 (thickness between the flat surfaces n) is 1.5 to 5 mm
- the length of the support 2 in the L direction is 100 to 150 mm.
- the shape of the support body 2 should just be column shape, and is not limited to the hollow flat plate type of FIG.1, 4, A cylindrical shape and a flat plate type may be sufficient.
- the fuel electrode layer 8 causes an electrode reaction, and is a porous conductive ceramic in this embodiment.
- a material composed of ZrO 2 and Ni and / or NiO in which a rare earth element is dissolved or a material composed of CeO 2 and Ni and / or NiO in which another rare earth element is dissolved.
- the rare earth element the rare earth elements exemplified in the support 2 can be used, and examples thereof include a material made of ZrO 2 (YSZ) in which Y is dissolved and Ni and / or NiO.
- the content of ZrO 2 in which the rare earth element in the fuel electrode layer 8 is dissolved or the content of CeO 2 in which the other rare earth element is dissolved is in the range of 35 to 65% by volume, and the content of Ni or NiO The amount is 65-35% by volume. Further, the open porosity of the fuel electrode layer 8 is 15% or more, particularly in the range of 20 to 40%, and the thickness thereof is 1 to 30 ⁇ m.
- the fuel electrode layer 8 since the fuel electrode layer 8 only needs to be disposed at a position facing the oxygen electrode layer 10, for example, the fuel electrode layer 8 does not extend to the upper flat surface n and the arcuate surface m in FIG.
- the fuel electrode layer 8 may be disposed only on the lower flat surface n.
- the electrolyte layer 9 has a function as an electrolyte for bridging electrons between the fuel electrode layer 8 and the oxygen electrode layer 10, and at the same time has a gas barrier property to prevent leakage between the fuel gas and the oxygen-containing gas. It is required to have In this embodiment, ceramic (solid oxide) made of partially stabilized or stabilized ZrO 2 containing 3 to 15 mol% of a rare earth element such as Y, Sc, or Yb is used. Y is used as the rare earth element because it is inexpensive.
- the electrolyte layer 9 may be made of, for example, a LaGaO 3 -based material, and may be made of other materials as long as it has the above characteristics. In this embodiment, the thickness of the electrolyte layer 9 is 20 to 40 ⁇ m. Particularly, in order to suppress gas permeation in the electrolyte layer 9, the thickness of the electrolyte layer is 30 to 40 ⁇ m.
- the interconnector layer 11 is made of conductive ceramics. Since it is in contact with fuel gas (hydrogen-containing gas) and oxygen-containing gas, it has reduction resistance and oxidation resistance. For this reason, the interconnector layer 11 is generally made of a LaCrO 3 -based perovskite oxide. In particular, the LaCrMgO 3 system in which Mg is present at the B site for the purpose of approaching the thermal expansion coefficients of the support 2 and the electrolyte layer 9. An oxide is used, but is not limited to the above materials.
- the interconnector layer 11 must be dense to prevent leakage of fuel gas flowing through the gas flow path 13 formed in the support 2 and oxygen-containing gas flowing outside the support 2. However, in this embodiment, it has a relative density of 93% or more, particularly 95% or more. In the present embodiment, the thickness of the interconnector layer 11 is 10 to 50 ⁇ m from the viewpoint of gas leakage prevention and electrical resistance.
- the adhesion layer (not shown) has a composition similar to that of the fuel electrode layer 8.
- a composition similar to that of the fuel electrode layer 8.
- a composition composed of Y 2 O 3 and Ni and / or NiO, a composition composed of ZrO 2 (YSZ) in which Y is solid-solved and Ni and / or NiO, Y, Sm, Gd and the like are solid.
- the composition can be mentioned consists of CeO 2 and Ni and / or NiO was dissolved.
- the volume ratio of ZrO 2 (CeO 2 ) in which rare earth oxide or rare earth element is dissolved and Ni and / or NiO is in the range of 40:60 to 60:40.
- Ni and / or NiO powder a rare earth oxide powder such as Y 2 O 3 , an organic binder, and a solvent are mixed to prepare a clay, and this clay is used for extrusion molding.
- a conductive support molded body is prepared and dried. Further, as the conductive support molded body, a calcined body calcined at 900 to 1000 ° C. for 2 to 6 hours may be used.
- raw materials of NiO and ZrO 2 (YSZ) in which Y 2 O 3 is dissolved are weighed and mixed. Thereafter, an organic binder and a solvent are mixed with the mixed powder to prepare a slurry for the fuel electrode layer.
- ZrO 2 powder in which the rare earth element was solid-dissolved was slurried by adding toluene, binder powder (below, polymer higher than binder powder attached to ZrO 2 powder, for example, acrylic resin), commercially available dispersant, and the like.
- binder powder lower, polymer higher than binder powder attached to ZrO 2 powder, for example, acrylic resin
- dispersant commercially available dispersant, and the like.
- the sheet is molded by a method such as a doctor blade to produce a sheet-like electrolyte layer molded body.
- a slurry for the fuel electrode layer is applied onto the obtained sheet-shaped electrolyte layer molded body and dried to form a fuel electrode layer molded body, thereby forming a sheet-shaped laminated molded body.
- the fuel electrode layer molded body side surface of the fuel electrode layer molded body and the electrolyte layer molded body on the fuel electrode layer molded body side is laminated on the conductive support molded body to form a molded body.
- an interconnector layer material for example, LaCrMgO 3 -based oxide powder
- an organic binder for example, LiCrMgO 3 -based oxide powder
- a solvent for example, a solvent
- a method for producing a cell having an adhesion layer will be described.
- the adhesion layer molded body located between the support body 2 and the interconnector layer 11 is formed.
- ZrO 2 in which Y is dissolved and NiO are mixed and dried so that the volume ratio is in the range of 40:60 to 60:40, an organic binder or the like is added to adjust the slurry for the adhesion layer, and the electrolyte layer
- the adhesion layer molded body is formed by applying the conductive support molded body between both ends of the molded body.
- an intermediate layer disposed between the electrolyte layer and the oxygen electrode layer is formed.
- CeO 2 powder in which GdO 1.5 is dissolved is heat-treated at 800 to 900 ° C. for 2 to 6 hours to prepare a raw material powder for the intermediate layer molded body, and toluene is added as a solvent thereto.
- an intermediate layer slurry is prepared, and this slurry is applied onto the electrolyte layer formed body to prepare an intermediate layer formed body.
- a sheet-like intermediate layer molded body may be prepared and laminated on the electrolyte layer molded body.
- the intermediate layer slurry is applied to the side of the sheet-shaped electrolyte layer molded body where the fuel electrode layer molded body is not formed and dried, and the fuel electrode layer molded body is formed on one side of the sheet-shaped electrolyte layer molded body.
- a sheet-like laminated molded body in which the intermediate layer molded body is formed on the other side may be produced, and the surface on the fuel electrode layer molded body side may be laminated on the conductive support molded body to form the molded body.
- the interconnector layer slurry is applied to the upper surface of the adhesion layer molded body so that both end portions of the interconnector layer molded body are laminated on both end portions of the electrolyte molded body, thereby producing a laminated molded body.
- the above-mentioned laminated molded body is debindered and simultaneously sintered (co-fired) in an oxygen-containing atmosphere at 1400 to 1450 ° C. for 2 to 6 hours.
- the interconnector layer slurry is prepared, the interconnector layer sheet is prepared, and the both ends of the interconnector layer sheet are laminated on both ends of the electrolyte layer molded body.
- An interconnector layer sheet can be laminated to produce a laminated molded body.
- an oxygen electrode layer material for example, LaCoO 3 oxide powder
- the pulverized particle size of the secondary raw material powder is adjusted so that the particle size distribution of the secondary particles is not sharp and has two or more peaks.
- the particle size distribution is adjusted such that D10 is 0.01 to 1 ⁇ m, D50 is 0.3 to 10 ⁇ m, and D90 is 5 to 50 ⁇ m.
- D10, D50, and D90 are particles that are 10%, 50%, and 90% of the total number of particles counted from a powder having a small particle size in the particle size distribution in the microtrack method of the secondary raw material powder. Means diameter.
- a method of adjusting the pulverization time of the raw material can also be adopted. A method of mixing and adjusting a secondary raw material that has been adjusted to coarse grains by re-calcining the adjusted fine secondary raw material is also included.
- the raw material powder of the oxygen electrode layer material is a raw material produced by a liquid phase synthesis method such as a coprecipitation method, a Petchini method (organic acid salt combustion method), or a citrate method. Powder is used.
- the raw material powder produced by the liquid phase synthesis method has high crystallinity, the presence of a by-product phase at the time of firing and cell operation, and the diffusion of atoms therein, and deformation of the particles constituting the oxygen electrode layer. Can be suppressed.
- a slurry containing a solvent and a pore-forming agent is applied to the surface of the intermediate layer with respect to the prepared raw material by dipping or printing, and baked at 1000 to 1200 ° C. for 2 to 6 hours.
- a layer is formed, and the cell 1 of this embodiment having the structure shown in FIG. 1 can be manufactured.
- the cell 1 is then preferably subjected to a reduction treatment of the support 2 and the fuel electrode layer 8 by flowing hydrogen gas therein. At that time, it is preferable to perform the reduction treatment at 750 to 1000 ° C. for 5 to 20 hours, for example.
- FIG. 4 shows an example of a cell stack device configured by electrically connecting a plurality of the above-described cells 1 in series via a current collecting member 13, and (a) shows a cell stack device.
- 18 is a side view schematically showing 18, and (b) is a cross-sectional view of the broken line portion of the cell stack device 18 of (a), and shows an excerpted portion surrounded by the broken line shown in (a). .
- the part corresponding to the part surrounded by the broken line shown in (a) is shown by an arrow, and in the cell 1 shown in (b), the intermediate layer 12 and the like described above are shown. A part of the members are omitted.
- the cell stack device 18 includes a cell stack 19 in which a plurality of cells 1 are juxtaposed and each cell 1 is connected by a current collecting member 13.
- an elastically deformable conductive member 14 is provided at both ends of the plurality of cells 1 in the juxtaposed direction, and the plurality of cells 1 juxtaposed are sandwiched.
- a current extraction unit 15 for extracting a current generated by the power generation of the cell stack 19 (cell 1) is connected to the conductive member 14. Further, the lower end of each cell 1 and the lower end of the conductive member 14 are fixed to the gas tank 16 with an adhesive such as a glass sealing material.
- the cell stack apparatus 18 of the present embodiment also includes the cell 1 described above, the cell stack apparatus 18 with improved long-term reliability can be obtained.
- FIG. 5 is an external perspective view showing an example of a fuel cell module 30 which is an example of an electrochemical module in which the cell stack device 18 is accommodated in a storage container, and inside the rectangular parallelepiped storage container 31, FIG. 2 shows a state before the cell stack device 18 shown in FIG. In other words, a part (front and rear surfaces) of the storage container 31 is removed, and the cell stack device 18 and the reformer 32 stored in the storage container 31 are taken out rearward.
- the cell stack device 18 can be slid and stored in the storage container 31.
- the fuel cell module 30 is provided with a reformer 32 for reforming raw fuel such as natural gas or kerosene to generate fuel gas in order to obtain fuel gas used in the cell 1, a fuel cell stack. Located above the device 18. The fuel gas generated by the reformer 32 is supplied to the gas tank 16 through the gas flow pipe 33 and is supplied from the gas tank 16 to the gas passage 2 provided inside the cell 1.
- a reformer 32 for reforming raw fuel such as natural gas or kerosene to generate fuel gas in order to obtain fuel gas used in the cell 1, a fuel cell stack.
- the oxygen-containing gas introduction member 35 provided inside the storage container 31 is disposed between a pair of fuel cell stack devices 18 juxtaposed in the gas tank 16 in FIG. Then, the oxygen-containing gas is supplied to the lower end portion of the cell 1 so that the oxygen-containing gas flows sideways from the lower end portion toward the upper end portion in accordance with the flow of the fuel gas. Moreover, the temperature of the cell 1 is raised by reacting the fuel gas discharged from the gas passage 2 of the cell 1 shown in FIG. 1A with the oxygen-containing gas and burning it on the upper end side of the cell 1. Thus, the activation of the cell stack device 18 can be accelerated.
- the fuel gas discharged from the gas passage 3 of the cell 1 and the oxygen-containing gas are combusted on the upper end side of the cell 1 so as to be disposed above the cell 1 (fuel cell stack device 18).
- the reformer 32 can be warmed. Thereby, the reforming reaction can be efficiently performed in the reformer 32.
- the fuel cell module 30 of the present embodiment since the cell stack device 18 described above is housed in the housing container 31, the fuel cell module 30 with improved long-term reliability can be obtained.
- FIG. 6 shows an example of a fuel cell device which is an example of an electrochemical device in which the fuel cell module 30 shown in FIG. 5 and an auxiliary machine for operating the fuel cell module 30 are housed in an outer case. It is a perspective view. In FIG. 6, a part of the configuration is omitted.
- the fuel cell device 40 shown in FIG. 6 divides the inside of the outer case composed of the support column 41 and the outer plate 42 by a partition plate 43, and the upper side thereof is a module storage chamber for storing the fuel cell module 30 described above. 44, and the lower side is configured as an auxiliary equipment storage chamber 45 for storing auxiliary equipment for operating the fuel cell module 30. Note that the auxiliary machines stored in the auxiliary machine storage chamber 44 are not shown.
- the partition plate 43 is provided with an air circulation port 46 for allowing the air in the auxiliary machine storage chamber 45 to flow toward the module storage chamber 44, and a part of the exterior plate 42 constituting the module storage chamber 44, An exhaust port 47 for exhausting air in the module storage chamber 44 is provided.
- the fuel cell module 30 that can improve the reliability is housed in the module housing chamber 44, thereby improving the reliability. 40.
- the present invention is not limited to the above-described embodiment, and various modifications and improvements can be made without departing from the scope of the present invention.
- it may be a fuel battery cell in which an oxygen electrode layer, an electrolyte layer, and a fuel electrode layer are arranged in this order on a conductive support.
- the fuel electrode layer 8, the electrolyte layer 9, and the oxygen electrode layer 10 are laminated on the outer periphery of the support 2.
- the support 2 is not necessarily required or supports that also serve as the fuel electrode layer. It may be a body.
- the hollow plate type electrolyte fuel cell has been described.
- the plate type electrolyte fuel cell may be a cylindrical type electrolyte fuel cell. is there.
- Various intermediate layers may be additionally provided between the members in accordance with the function.
- the fuel cell, the cell stack device using the same, the fuel cell module, and the fuel cell device have been described.
- the present invention is not limited to this, and water vapor and voltage are applied to the cell.
- the present invention can also be applied to an electrolysis cell (SOEC) that generates hydrogen and oxygen (O 2 ) by electrolyzing water vapor (water), and an electrolysis cell stack device, an electrolysis module, and an electrolysis device including the electrolysis cell.
- SOEC electrolysis cell
- O 2 hydrogen and oxygen
- a NiO powder having an average particle size of 0.5 ⁇ m and a Y 2 O 3 powder having an average particle size of 0.9 ⁇ m are mixed, and a clay prepared with an organic binder and a solvent is molded by an extrusion molding method and dried.
- a conductive support molded body was prepared by degreasing. The conductive support molded body had a volume ratio after firing and reduction of 48% by volume of NiO and 52% by volume of Y 2 O 3 .
- a binder powder (low molecular weight) made of an acrylic resin is added to ZrO 2 powder (electrolyte layer raw material powder) having a particle size of 0.8 ⁇ m in which 8 mol% of Y is solid-dissolved by the microtrack method.
- An electrolyte layer sheet was prepared by a doctor blade method using a slurry obtained by mixing a layer raw material powder, a binder powder (high molecular weight) made of an acrylic resin, and a solvent.
- a complex oxide containing 90 mol% of CeO 2 and 10 mol% of rare earth element oxide (GdO 1.5 , SmO 1.5 ) is pulverized with a vibration mill or ball mill using isopropyl alcohol (IPA) as a solvent. Then, calcination treatment is performed at 900 ° C. for 4 hours, pulverization treatment is performed again with a ball mill, the degree of aggregation of the ceramic particles is adjusted, and an acrylic binder and toluene are added to and mixed with this powder, A slurry for forming an intermediate layer molded body was prepared.
- IPA isopropyl alcohol
- a slurry for a fuel electrode layer in which a NiO powder having an average particle size of 0.5 ⁇ m, a ZrO 2 powder in which Y 2 O 3 is solid-solved, an organic binder, and a solvent are mixed is prepared, and a screen printing method is performed on the electrolyte layer sheet.
- a screen printing method is performed on the electrolyte layer sheet.
- a slurry for forming the intermediate layer formed body is applied by screen printing on the electrolyte layer sheet on the surface opposite to the surface on which the fuel electrode layer formed body is formed, and dried. A layer compact was formed.
- a conductive support with a sheet-like laminated molded body in which an intermediate layer molded body and a fuel electrode layer molded body are formed on both surfaces of the electrolyte layer sheet, with the fuel electrode layer molded body side facing inside (support side) Laminated in place on the body.
- the laminated molded body in which the molded bodies were laminated as described above was calcined at 1000 ° C. for 3 hours.
- the La (Mg 0.3 Cr 0.7) 0.96 O 3 to prepare a slurry for the interconnector obtained by mixing an organic binder and a solvent. Furthermore, the raw material which consists of Ni and YSZ was mixed and dried, the organic binder and the solvent were mixed, and the slurry for adhesion layers was adjusted. The adjusted slurry for the adhesion layer is applied to the portion of the conductive support where the fuel electrode layer (and the electrolyte layer) is not formed (the portion where the conductive support is exposed), and the adhesion layer formed body is laminated and adhered. The interconnector layer slurry was applied on the layered product. Then, the above-mentioned laminated molded body was subjected to binder removal treatment and co-fired at 1450 ° C. for 2 hours in an oxygen-containing atmosphere.
- La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder having an average particle diameter of 10 ⁇ m prepared by a liquid phase synthesis method using a citrate method was pulverized with a ball mill, and sample No. .
- the secondary raw material powder obtained by recalcining the pulverized powder at a predetermined temperature and pulverized for a predetermined time was used as the secondary raw material powder for the oxygen electrode layer. It adjusted so that it might become.
- a binder, isopropyl alcohol, and a pore former are added to this to produce a paste, which is applied to the surface of the intermediate layer of the laminated sintered body by a screen printing method to form an oxygen electrode layer molded body.
- the cell shown in FIG. 1 was produced by baking at 1100 ° C. for 4 hours to form an oxygen electrode layer.
- Sample No. For No. 9, a secondary raw material powder produced by spray pyrolysis was used.
- the size of the produced cell is 25 mm ⁇ 200 mm, the thickness of the conductive support (thickness between the flat surfaces n) is 2 mm, the open porosity is 35%, the thickness of the fuel electrode layer is 10 ⁇ m, the open porosity is 24%, the electrolyte
- the layer thickness was 50 ⁇ m.
- the thickness of the oxygen electrode layer was 100 ⁇ m, and the overall porosity of the oxygen electrode layer was adjusted to a range of 30 to 35%. Tables 1 and 2 show the results of measurement such as pore distribution in the oxygen electrode layer.
- each member was obtained from a photograph of a scanning electron microscope (SEM) for the thickness of the oxygen electrode layer in the flat portion of the conductive support.
- SEM scanning electron microscope
- the structure of the oxygen electrode layer is observed with a scanning electron microscope (SEM) at a magnification of 500 times, the pores in one field of view are specified, the pore area is calculated in terms of a circle, and the pore diameter is calculated. Then, the pore size distribution of the low magnification observation (second pore and third pore) is obtained from the number and the number, and then the magnification of the SEM is increased to 3000 times and the same operation as the low magnification observation is performed to perform the high magnification observation (first pore). ) was determined.
- SEM scanning electron microscope
- the shape of each pore was measured with an image analysis apparatus for each of five SEM photographs by the method described above for an arbitrary polished cross section, and the average aspect ratio of the first and second pores.
- the first pores were calculated by extracting the first pores having a pore size at the lower limit of the first peak from the pore size corresponding to the maximum value of the first peak from a 3000 times SEM photograph.
- the second pore was calculated by extracting the second pore having the upper limit pore diameter of the second peak from the pore diameter corresponding to the maximum value of the second peak from the 500 times SEM photograph.
- the structure was observed at any five locations in the oxygen electrode layer by SEM observation at 500 times, and the abundance ratio of the porous portion, the dense portion, and the void portion was determined based on the above-described determination method. Furthermore, the boundary between the porous portion and the dense portion was specified, and the shape of the dense portion was specified. In the table, the square of the outer peripheral length of the dense part / the area of the dense part was described as “outer peripheral length 2 / area”.
- the power generation performance was evaluated using the obtained cell.
- the power density (0.3 A / cm 2 , 750 ° C.) of the cell at the initial stage of power generation was measured, and the reduction rate of the power density of the cell after operating for 1000 hours with respect to the power density at the initial stage of power generation was also measured. Further, the amount of potential drop indicating an increase in the actual resistance of the cell after operating for 1000 hours with respect to the initial stage of power generation was evaluated.
- initial power density, power density decrease rate, and potential drop amount are described. The results are shown in Table 2.
- Sample No. provided with an oxygen electrode layer prepared using a powder calcined at a predetermined recalcination temperature using a predetermined secondary raw material particle.
- the initial performance in power generation performance evaluation was high and the performance degradation was small.
- the sample No. 1 has three peaks in the pore size distribution, and the maximum value p1t of the first pore size is 0.15 ⁇ m or more.
- the potential drop of the cell after 1000 hours of operation was suppressed, and the Sr concentration distribution of the oxygen electrode layer was measured with an electron beam microanalyzer (EPMA) for samples 1 to 5 and 10.
- EPMA electron beam microanalyzer
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Abstract
Description
近年、次世代エネルギーとして、燃料ガス(水素含有ガス)と酸素含有ガス(通常、空気である)とを用いて電力を得ることができる燃料電池セルが開発されている。燃料電池セル(以下、セルということがある。)は、固体電解質層を燃料極層と酸素極層とで挟んだ構造を有している。セルは、燃料極層に燃料ガスを、酸素極層に酸素含有ガスを流し、セルを1000~1050℃に加温することによって発電する(例えば特許文献1参照)。
図1は、本実施形態の固体酸化物形のセル1の一例を示すものであり、(a)はその横断面図、(b)は(a)のインターコネクタ層側から見た側面図である。なお、両図面において、セル1の各構成の一部を拡大して示している。
本実施態様の酸素極層10は、いわゆるABO3型のペロブスカイト型酸化物からなる導電性セラミックスからなる。例えば、かかるペロブスカイト型酸化物として、Laを含有する遷移金属ペロブスカイト型酸化物、特にAサイトにSrが共存するLaMnO3系酸化物、LaFeO3系酸化物、LaCoO3系酸化物の少なくとも1種が挙げられ、600~1000℃程度の作動温度での電気伝導性が高いという点からLaCoO3系酸化物がよい。なお、このペロブスカイト型酸化物においては、Bサイトに、CoとともにFeやMnが固溶するものであっても良い。
以上説明した本実施形態のセル1の作製方法の一例について説明する。
酸素極層を形成する二次原料粒子の粒度分布をこのような範囲に調整するためには、原料の粉砕時間を調整する方法も採用することができるが、場合によっては、均一な粒度分布に調整した微粒な二次原料に対して、再仮焼等を行って全体を粗粒に調整した二次原料を混合して調整する方法も挙げられる。
図4は、上述したセル1の複数個を、集電部材13を介して電気的に直列に接続して構成されたセルスタック装置の一例を示したものであり、(a)はセルスタック装置18を概略的に示す側面図、(b)は(a)のセルスタック装置18の破線部についての横断面図であり、(a)で示した破線で囲った部分を抜粋して示している。なお、(b)において(a)で示した破線で囲った部分に対応する部分を明確とするために矢印にて示しており、(b)で示すセル1においては、上述した中間層12等の一部の部材を省略して示している。
図5は、セルスタック装置18を収納容器内に収納してなる電気化学モジュールの一例である燃料電池モジュール30の一例を示す外観斜視図であり、直方体状の収納容器31の内部に、図4に示したセルスタック装置18を収納する前の状態を示している。すなわち収納容器31の一部(前後面)を取り外し、内部に収納されているセルスタック装置18および改質器32を後方に取り出した状態で示している。図5に示した燃料電池モジュール30においては、セルスタック装置18を、収納容器31内にスライドして収納することが可能である。
図6は、外装ケース内に図5で示した燃料電池モジュール30と、燃料電池モジュール30を動作させるための補機とを収納してなる電気化学装置の一例である燃料電池装置の一例を示す斜視図である。なお、図6においては一部構成を省略して示している。
2:導電性支持体(支持体)
3:燃料ガス通路
8:燃料極層
9:電解質層
10:酸素極層
11:インターコネクタ層
12:中間層
20:第1気孔
21:第2気孔
22:第3気孔
24:ポーラス部
25:緻密部
26:空隙部
p1 第1ピーク
p2 第2ピーク
p3 第3ピーク
p1t 第1ピークの最大値
p2t 第2ピークの最大値
p3t 第3ピークの最大値
Claims (12)
- 固体酸化物形の電解質層の一方主面に燃料極層を、他方主面に酸素極層を配置してなり、前記酸素極層は複数の気孔を有し、前記酸素極層の任意断面にて観察される前記気孔の気孔径分布において3つ以上のピークを有するセル。
- 前記3つ以上のピークが、気孔径0.02~1μmの範囲にピークの最大値が存在する第1ピークと、気孔径1~5μmの範囲にピークの最大値が存在する第2ピークと、気孔径4~25μmの範囲にピークの最大値が存在する第3ピークとからなる請求項1記載のセル。
- 前記第1ピークの面積比率が80~90%、前記第2ピークの面積比率が9~19%、前記第3ピークの面積比率が0.3~2%である請求項2記載のセル。
- 前記第1ピークの最大値が気孔径0.15~0.6μmの範囲に存在する請求項2または3記載のセル。
- 前記複数の気孔は、前記第1ピークの範囲内にある第1気孔と、前記第2ピークの範囲内にある第2気孔と、前記第3ピークの範囲内にある第3気孔とからなり、前記第2ピークの範囲内にある気孔は、アスペクト比が3~10の扁平気孔を含む請求項2乃至4のいずれかに記載のセル。
- 前記酸素極層は、該酸素極層の任意断面を観察したとき、ポーラス部と緻密部と空隙部とからなり、前記ポーラス部は、前記第1気孔のそれぞれを中心として半径が前記第1ピークの最大値に対応する気孔径の3倍の円をそれぞれ描き、該円の中に含まれる気孔の面積が15%以上となる円が重畳して形成される集合体のうち、最も外側に位置する前記円の中心同士をつないで囲まれる領域であり、前記空隙部は気孔径が10μm以上の気孔からなる領域であり、前記緻密部は前記ポーラス部および前記空隙部を除く領域である請求項2乃至5のいずれかに記載のセル。
- 前記緻密部は、当該緻密部の外周長さが前記第1ピークの最大値に対応する気孔径の10倍以上である請求項6記載のセル。
- 前記緻密部は、当該緻密部の面積に対する当該緻密部の外周長さの2乗の値が40~100である請求項6または7記載のセル。
- 前記ポーラス部が25~55面積%、前記緻密部が15~35面積%、前記空隙部が10~60面積%の割合で存在する請求項6乃至8のいずれかに記載のセル。
- 請求項1乃至9のいずれかに記載のセルの複数を、集電部材を介して電気的に接続してなるセルスタックを具備するセルスタック装置。
- 請求項10に記載のセルスタック装置が、収納容器内に収納されてなる電気化学モジュール。
- 請求項11に記載の電気化学モジュールを具備する電気化学装置。
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CN201380025110.7A CN104321916B (zh) | 2012-05-31 | 2013-05-31 | 电池单元及电池堆装置以及电化学模块、电化学装置 |
EP13797628.8A EP2858152A4 (en) | 2012-05-31 | 2013-05-31 | CELL, CELL STACKING DEVICE, ELECTROCHEMICAL MODULE, AND ELECTROCHEMICAL DEVICE |
US14/404,482 US10355282B2 (en) | 2012-05-31 | 2013-05-31 | Cell, cell stack unit, electrochemical module, and electrochemical apparatus |
US16/430,468 US11450859B2 (en) | 2012-05-31 | 2019-06-04 | Cell, cell stack unit, electrochemical module, and electrochemical apparatus |
US17/881,650 US11909051B2 (en) | 2012-05-31 | 2022-08-05 | Cell, cell stack unit, electrochemical module, and electrochemical apparatus |
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US16/430,468 Continuation US11450859B2 (en) | 2012-05-31 | 2019-06-04 | Cell, cell stack unit, electrochemical module, and electrochemical apparatus |
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Cited By (2)
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JP2016157693A (ja) * | 2015-02-25 | 2016-09-01 | 日本特殊陶業株式会社 | 固体酸化物形燃料電池単セル及び固体酸化物形燃料電池スタック |
JP2017130327A (ja) * | 2016-01-20 | 2017-07-27 | 日本特殊陶業株式会社 | 電気化学反応単セル、インターコネクタ−電気化学反応単セル複合体、および、電気化学反応セルスタック |
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SG11201801391QA (en) * | 2015-08-31 | 2018-03-28 | Kyocera Corp | Fuel cell module and fuel cell apparatus |
US20190044165A1 (en) * | 2017-08-04 | 2019-02-07 | Bloom Energy Corporation | Cerium oxide treatment of fuel cell components |
JP2023144948A (ja) * | 2022-03-28 | 2023-10-11 | 大阪瓦斯株式会社 | 固体酸化物形電解セル、固体酸化物形電解セルの製造方法、固体酸化物形電解モジュール、電気化学装置及びエネルギーシステム |
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US10355282B2 (en) | 2019-07-16 |
EP2858152A1 (en) | 2015-04-08 |
JP2019071289A (ja) | 2019-05-09 |
US20150171432A1 (en) | 2015-06-18 |
US20190288296A1 (en) | 2019-09-19 |
US11450859B2 (en) | 2022-09-20 |
CN104321916A (zh) | 2015-01-28 |
US11909051B2 (en) | 2024-02-20 |
JP2017191786A (ja) | 2017-10-19 |
CN104321916B (zh) | 2017-05-17 |
EP2858152A4 (en) | 2016-01-27 |
US20220393183A1 (en) | 2022-12-08 |
JP6473780B2 (ja) | 2019-02-20 |
JPWO2013180299A1 (ja) | 2016-01-21 |
JP6174577B2 (ja) | 2017-08-02 |
DE202013012667U1 (de) | 2018-04-30 |
JP6698892B2 (ja) | 2020-05-27 |
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