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WO2018167889A1 - Électrode à oxygène pour cellule électrochimique, et cellule électrochimique - Google Patents

Électrode à oxygène pour cellule électrochimique, et cellule électrochimique Download PDF

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Publication number
WO2018167889A1
WO2018167889A1 PCT/JP2017/010500 JP2017010500W WO2018167889A1 WO 2018167889 A1 WO2018167889 A1 WO 2018167889A1 JP 2017010500 W JP2017010500 W JP 2017010500W WO 2018167889 A1 WO2018167889 A1 WO 2018167889A1
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Prior art keywords
electrochemical cell
oxide
oxygen electrode
phase
site
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Japanese (ja)
Inventor
憲和 長田
亀田　常治
吉野　正人
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Toshiba Corp
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Toshiba Corp
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Priority to PCT/JP2017/010500 priority Critical patent/WO2018167889A1/fr
Priority to JP2019505599A priority patent/JP6833974B2/ja
Publication of WO2018167889A1 publication Critical patent/WO2018167889A1/fr
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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
    • 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
    • H01M8/02—Details
    • 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
    • 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

Definitions

  • Embodiments of the present invention relate to an oxygen electrode for an electrochemical cell and an electrochemical cell.
  • Solid oxide electrochemical cells are being developed as fuel cells for power generation, electrolysis cells for hydrogen production, and power storage systems that combine these. Since the solid oxide electrochemical cell uses a solid oxide as an electrolyte, the operating temperature is high (for example, 600 to 1000 ° C.), and a high reaction rate can be obtained without using an expensive noble metal catalyst. Is possible. For this reason, when this is operated as a fuel cell (solid oxide fuel cell: SOFC), high power generation efficiency is obtained, and when it is operated as an electrolysis cell (solid oxide type electrolysis cell: SOEC), it is high at a low electrolysis voltage. Hydrogen can be produced efficiently.
  • SOFC solid oxide fuel cell
  • SOEC solid oxide type electrolysis cell
  • solid oxide electrochemical cells have a hydrogen electrode side as a support and an oxygen electrode formed on the support (hydrogen electrode support type).
  • the area of the oxygen electrode is smaller than that of the hydrogen electrode (the area of the electrode and effective reaction part is small), and the performance of the oxygen electrode effectively determines the performance of the entire cell. That is, it is important to improve the performance of the oxygen electrode in order to improve the performance or extend the life of the solid oxide electrochemical cell.
  • the problem to be solved by the present invention is to provide an oxygen electrode for an electrochemical cell and an electrochemical cell in which the performance of the oxygen electrode is improved.
  • the oxygen electrode for an electrochemical cell according to the embodiment is disposed in a predetermined region, is disposed in a predetermined region, and is dispersed in the predetermined region, and one constituent element is the first element. And a second oxide having a higher density than that of the oxide.
  • FIG. 4 is a SEM photograph of a cross section of an electrochemical cell in Example 3.
  • 4 is a Co distribution of an electrochemical cell cross section of Example 3.
  • FIG. 4 is an Fe distribution in a cross section of an electrochemical cell of Example 3.
  • 4 is a La distribution of a cross section of an electrochemical cell of Example 3. It is Sr distribution of the electrochemical cell cross section of Example 3.
  • FIG. It is Gd distribution of the electrochemical cell cross section of Example 3.
  • It is Ce distribution of the electrochemical cell cross section of Example 3.
  • FIG. It is a SEM photograph of the electrochemical cell cross section of a comparative example. It is Co distribution of the electrochemical cell cross section of a comparative example.
  • the present invention is not limited to the following embodiment and examples.
  • the schematic diagram referred in the following description is a figure which shows the positional relationship of each structure, The ratio of the magnitude
  • FIG. 1 is a cross-sectional view schematically showing a part of a cross-sectional structure of a flat plate type solid oxide electrochemical cell 10.
  • the flat plate type solid oxide electrochemical cell 10 is a hydrogen electrode supported solid oxide electrochemical cell.
  • a hydrogen electrode 12, an electrolyte layer 13, a reaction preventing layer 14, and an oxygen electrode 15 are sequentially laminated.
  • the support substrate 11, the hydrogen electrode 12, and the oxygen electrode 15 are porous and allow gas (gas) to pass therethrough.
  • the electrolyte layer 13 and the reaction preventing layer 14 do not need to pass gas (pass ions) and are dense (non-porous).
  • a reducing agent such as hydrogen supplied to the hydrogen electrode 12 and an oxidizing agent such as oxygen supplied to the oxygen electrode 15 react electrochemically to generate electric energy and water vapor.
  • an oxidizing agent such as oxygen supplied to the oxygen electrode 15 react electrochemically to generate electric energy and water vapor.
  • water vapor or the like is reduced by electrolysis at the hydrogen electrode 12, and oxygen is released from the oxygen electrode 15.
  • the support substrate 11 is a layer serving as a support for the electrochemical cell 10, and the mechanical strength of the electrochemical cell 10 can be maintained or improved.
  • the constituent material of the support substrate 11 can be the same as the constituent material of the next hydrogen electrode 12.
  • the hydrogen electrode 12 can be composed of a sintered body containing metal (catalyst) particles and a metal oxide (oxygen ion conductive oxide).
  • the metal include one or more selected from the group consisting of nickel, cobalt, iron and copper, or alloys containing them.
  • the metal oxide include stabilized zirconia (SZ) and doped ceria (DC). In the stabilized zirconia, one or more kinds of stabilizers selected from the group consisting of Y 2 O 3 , Sc 2 O 3 , Yb 2 O 3 , Gd 2 O 3 , CaO, MgO, CeO 2 and the like are dissolved.
  • the doped ceria is ceria (cerium oxide: CeO 2 ) in which one or more oxides selected from the group consisting of Sm 2 O 3 , Gd 2 O 3 , Y 2 O 3, and the like are dissolved.
  • the electrolyte layer 13 is a solid oxide layer having electronic insulation and oxygen ion conductivity, and can be composed of, for example, stabilized zirconia (SZ) or doped ceria (DC).
  • SZ stabilized zirconia
  • DC doped ceria
  • the stabilized zirconia one or more stabilizers selected from the group consisting of Y 2 O 3 , Sc 2 O 3 , Yb 2 O 3 , Gd 2 O 3 , CaO, MgO, CeO 2 and the like are dissolved.
  • the reaction preventing layer 14 can be made of doped ceria (DC).
  • DC doped ceria
  • one or more oxides selected from the group consisting of Sm 2 O 3 , Gd 2 O 3 and Y 2 O 3 are solid-dissolved.
  • the reaction preventing layer 14 prevents the reaction between the electrolyte layer 13 and the oxygen electrode 15.
  • the oxygen electrode 15 and the electrolyte layer 13 may react to reduce the performance of the solid oxide electrochemical cell 10.
  • the oxygen electrode 15 and the electrolyte layer 13 are LaCoO 3 -based perovskite oxide and stabilized zirconia, respectively, a solid phase reaction is caused by firing to form a high resistance phase such as La 2 Zr 2 O 7 .
  • the reaction preventing layer 14 between the electrolyte layer 13 and the oxygen electrode 15, the solid phase reaction between the electrolyte layer 13 and the oxygen electrode 15 is prevented, and the performance of the solid oxide electrochemical cell 10 is ensured. it can.
  • the oxygen electrode 15 is composed of a sintered body containing a perovskite oxide.
  • Perovskite oxide is mainly represented by the following composition formula (1).
  • Ln include rare earth elements such as La.
  • A include Sr, Ca, and Ba.
  • B and C include Cr, Mn, Co, Fe, and Ni.
  • LaMnO 3 system lanthanum-manganese oxide
  • LaCoO 3 system lanthanum-cobalt oxide
  • the perovskite oxide can also be represented by the following composition formula (2).
  • ABO 3 Composition formula (2) “A” in the composition formula (2) corresponds to “Ln” and “A” in the composition formula (1).
  • “B” in the composition formula (2) corresponds to “B” and “C” in the composition formula (1).
  • the elements of Ln, A in the composition formula (1) (A in the composition formula (2)) belong to the A site, and elements B and C in the composition formula (1) (B in the composition formula (2)) belong to the B site. Belongs. As shown in the composition formula (1), when the amount of the element E1 at either the A site or the B site is large, the amount of the other element E2 belonging to the same site is reduced. This is to stabilize the perovskite structure.
  • the oxygen electrode 15 may contain doped ceria (DC) in addition to the perovskite oxide.
  • DC doped ceria
  • one or more oxides selected from the group consisting of Sm 2 O 3 , Gd 2 O 3 and Y 2 O 3 are solid-dissolved.
  • the oxide constituting the oxygen electrode 15 is divided into a first phase 151 (first oxide) and a second phase 152 (second oxide).
  • the first phase 151 is disposed in a continuous region of the entire layer of the oxygen electrode 15.
  • the second phase 152 is discretely (distributed) disposed in the first phase 151. As will be described later, by mixing the first and second phases 151 and 152, the performance of the oxygen electrode 15 can be improved and the life can be extended.
  • the first and second phases 151 and 152 have different element ratios in at least one of the A site and B site of the perovskite oxide as shown below.
  • the first phase 151 Ln 1-x1 A x1 B 1-y1 C y O 3- ⁇ 1
  • the first phase 152 Ln 1-x2 A x2 B 1-y2 C y O 3- ⁇ 2 That is, if any of x1 ⁇ x2 and y1 ⁇ y2 is established, the ratio of elements is different in either the A site (Ln, A) or the B site (B, C).
  • the second phase 152 is more Co and less Fe than the first phase 151 (x1 ⁇ x2 ), Or when La is large and Sr is small (y1 ⁇ y2).
  • the effect does not stop at the same site, but may affect another site.
  • Ln is lanthanum La and A, B, and C are Sr, Co, and Fe, respectively
  • the second phase 152 is more Co and less Fe, La, and Sr than the first phase 151. It is possible.
  • the coexistence of the first and second phases 151 and 152 may be difficult (the second phase 152 may become unstable).
  • the first and second phases 151 and 152 can coexist.
  • the first phase 151 has an ABO 3 structure (Ln 1-x A x B 1-y C y O 3- ⁇ structure).
  • the second phase 152 may have an A 2 BO 4 structure or a B 3 O 4 structure in addition to the ABO 3 structure.
  • first, second phases 151 and 152 in addition to a combination of ABO 3 structure -ABO 3 structure, ABO 3 structure -A 2 BO 4 structure, a combination of ABO 3 structure -B 3 O 4 structure Even if it exists, the 1st, 2nd phase 151,152 may exist stably. This is considered to be because the first and second phases 151 and 152 settle in a stable state during the firing process when the solid oxide electrochemical cell 10 is formed.
  • Examples of the A 2 BO 4 structure include La 2-x Sr x Co 1-y Fe y O 4 and are represented by the following composition formula (3).
  • An example of the B 3 O 4 structure is Co 3-x Fe x O 4 and is represented by the following composition formula (4).
  • Ln is, for example, a rare earth element such as La.
  • Examples of A include Sr, Ca, and Ba.
  • Examples of B and C include Cr, Mn, Co, Fe, and Ni.
  • the second phase 152 may have a single structure of any one of ABO 3 , A 2 BO 4 , and B 3 O 4 structures. Further, two or more of ABO 3 , A 2 BO 4 , and B 3 O 4 structures may be included.
  • the second phase 152 may exist in the ABO 3 , A 2 BO 4 , and B 3 O 4 structure with oxides having a plurality of composition ratios intermingled. That is, the variables x, y, and ⁇ in the composition formulas (1), (3), and (4) may not be constant within the same structure of the second phase 152.
  • one of the constituent elements is more in the second phase 152 than in the first phase 151.
  • the element E2 at the same site as the element E1 is smaller in the second phase 152 than in the first phase 151 as described above.
  • the density ratios of the first and second phases 151 and 152 are ⁇ 1 and ⁇ 2, respectively, the density ratio ⁇ 2 is larger than the density ratio ⁇ 1 ( ⁇ 2> ⁇ 1).
  • This ratio R is greater than 1. It is preferable that the ratio R is a somewhat large value, for example, 1.5 or more (more preferably 2.0 or more). When the ratio R is close to 1, the difference between the first and second phases 151 and 152 is small, and even if the phases are mixed, it is difficult to improve performance.
  • the outer shape of the second phase 152 is circular (spherical), but actually, the outer shape of the second phase 152 is an intricate shape with irregularities due to stabilization such as a perovskite structure. Rather, it is considered that an intricate shape is preferable from the viewpoint of improving the performance of the oxygen electrode 15 by increasing the interface between the first and second phases 151 and 152.
  • the size of the second phase 151 can be evaluated by a virtual diameter (particle diameter, diameter) D.
  • the virtual diameter D is defined by the following equation (1).
  • D 2 ⁇ (S / ⁇ ) 1/2 ... formula (1)
  • the area S is the area of each second phase 152 on the sample cross section.
  • a set of bright spots in FIG. 2B described later corresponds to the second phase 152.
  • yen (dotted line) surrounding the 2nd phase 152 in FIG. 2B shows each 2nd phase 152 (2nd oxide), and is unrelated to the virtual diameter D.
  • the size (virtual diameter D) of the second phase 152 is preferably 100 nm or more and 5000 nm or less (more preferably 0.3 ⁇ m or more and 3 ⁇ m or less). If the size is too small, the stability of the phase may be lacking. If the size is too large, the performance of the oxygen electrode 15 may be improved due to an increase in the interface between the first and second phases 151 and 152.
  • the density of the second phase 152 is preferably 10 pieces / mm 2 or more and about 10,000 pieces / mm 2 or less (more preferably, 500 pieces / mm 2 or more and about 5000 pieces / mm 2 or less). Even if the density is too small or too large, the performance of the oxygen electrode 15 is reversed.
  • third phases having different compositions may be dispersedly arranged.
  • the third phase can be an oxide having any one of the ABO 3 structure, the A 2 BO 4 structure, and the B 3 O 4 structure.
  • the presence of the second phase 152 can be confirmed by measuring the composition distribution.
  • a scanning electron microscope (SEM) capable of energy dispersive X-ray spectroscopy (EDX) can be used.
  • SEM scanning electron microscope
  • EDX energy dispersive X-ray spectroscopy
  • a solid oxide electrochemical cell is cleaved and the cross section is smoothed by ion milling or the like. This sample cross section is observed by SEM at a magnification of about 1000 to 100,000 times and measured by EDX.
  • the minimum composition measurement region for example, a radius of about 500 nm or less
  • the energy resolution for example, about 100 eV or less
  • the second phase 152 can be detected as follows, for example.
  • (1) Element Aggregation Detection As described above, the composition of the sample cross-section is analyzed, and the region of the element E1 aggregate (the first virtual diameter D) is a certain size (eg, 0.3 ⁇ m or more) 2 phase 152) (for example, in a circle (dotted line) in FIG. 2B described later).
  • the following methods (a) and (b) can be used.
  • the structure of the first and second phases 151 and 152 can be created by mixing a plurality of materials M1 and M2.
  • the powder material M1 corresponding to the first phase 151 and the powder material M2 corresponding to the second phase 152 are mixed and spray coated.
  • the powder material M2 has a larger proportion of at least a specific element, a larger particle size, and a smaller mixing amount than the powder material M1.
  • the powder material M1 has a structure in which particles of the powder material M2 are dispersed.
  • the oxygen electrode 15 having the first and second phases 151 and 152 can be created by adjusting the heat treatment temperature. Specifically, heat treatment is performed in a state where the constituent materials of the electrolyte layer 13 and the reaction preventing layer 14 are laminated (primary heat treatment), and further, the heat treatment is performed by laminating the constituent materials of the oxygen electrode 15 (secondary heat treatment).
  • the temperature of the primary and secondary heat treatment is made higher than the normal temperature for forming the perovskite oxide.
  • the oxygen electrode 15 having the first and second phases 151 and 152 can be formed. This is due to thermal diffusion in two stages (thermal diffusion occurs between the electrolyte layer 13 and the reaction prevention layer 14 in the primary heat treatment, and thermal diffusion occurs between the reaction prevention layer 14 and the oxygen electrode 15 in the secondary heat treatment). It is considered a thing.
  • Example 1 A Preparation Sample 1 was prepared by the following procedures (1) to (5).
  • Nickel oxide (NiO) powder and gadolinium-doped ceria (GDC) powder are mixed at a weight ratio of 6: 4 to prepare a mixed powder.
  • the GDC is ceria (cerium oxide (IV): CeO 2) Gadoria to (gadolinium oxide: Gd 2 O 3) a (Gd 2 O 3) 0.1 mixed so that the composition of (CeO 2) 0.9 It is created by firing.
  • the precursor of the support substrate 11 is created by mixing the mixed powder with a solvent to form a paste and making this into a sheet shape.
  • the hydrogen electrode 12 is formed by mixing a mixed powder of nickel oxide (NiO) and gadolinium doped ceria (GDC) with a solvent and spray coating.
  • the electrolyte layer 13 is formed by mixing yttria-stabilized zirconia (YSZ) powder with a solvent and spray coating.
  • the reaction preventing layer 14 is formed by mixing GDC with a solvent and spray coating.
  • the primary laminate is fired at 1200 ° C. to 1600 ° C. (here, 1400 ° C.) until each layer and each layer have sufficient strength.
  • thermal diffusion occurs between the electrolyte layer 13 and the reaction preventing layer 14.
  • Evaluation Sample 1 was evaluated by the following procedures (1) and (2).
  • the hydrogen electrode output characteristic evaluation apparatus can evaluate the IV characteristics of the solid oxide electrochemical cell 10. That is, the water vapor concentration on the hydrogen electrode side is controlled, the solid oxide electrochemical cell 10 is operated in the SOFC mode and the SOEC mode, and the initial IV characteristics are measured. Thereafter, the temperature is lowered in a hydrogen atmosphere and cooled to room temperature, and the solid oxide electrochemical cell 10 is taken out from the hydrogen electrode output characteristic evaluation apparatus.
  • Example 2 A solid oxide electrochemical cell 10 was prepared in the same manner as in Example 1, and the IV characteristics in the initial state were evaluated. Thereafter, the solid oxide electrochemical cell 10 was continuously operated in the SOEC mode for about 250 hours. Further, the cross section was observed in the same manner as in Example 1.
  • Example 3 A solid oxide electrochemical cell 10 was prepared in the same manner as in Example 1, and the IV characteristics in the initial state were evaluated. Thereafter, the solid oxide electrochemical cell 10 was continuously operated in the SOEC mode for about 3000 hours. Further, the cross section was observed in the same manner as in Example 1.
  • Example 2 A solid oxide electrochemical cell was fabricated in substantially the same manner as in Example 1. However, the temperatures of the first and second heat treatments were lowered to 1300 ° C. and 1050 ° C., respectively. After evaluating the IV characteristics in the initial state, the solid oxide electrochemical cell 10 was continuously operated in the SOEC mode for about 3000 hours. Further, the cross section was observed in the same manner as in Example 1.
  • FIGS. 2A to 2G show the SEM photographs of the sample cross section of Example 3 and the results of surface analysis of Co, Fe, La, Sr, Gd, and Ce, respectively.
  • 3A to 3G respectively show SEM photographs of the cross-section of the sample of the comparative example and the results of surface analysis (EDX) of Co, Fe, La, Sr, Gd, and Ce.
  • 2A and 3A show states in which the cross sections of the electrolyte layer 13, the reaction preventing layer 14, and the oxygen electrode 15 are enlarged.
  • a dotted line is drawn at the boundary between the electrolyte layer 13, the reaction preventing layer 14, and the oxygen electrode 15. It can also be seen that the layer structure of the electrolyte layer 13, the reaction preventing layer 14, and the oxygen electrode 15 is formed, and the oxygen electrode 15 is porous.
  • the Co aggregate is clearly represented as a collection of bright spots.
  • this Co aggregate is surrounded by a circle (dotted line).
  • a portion (dark portion) where the density of Fe, La, and Sr is low exists at a position corresponding to the Co aggregate (circle (dotted line)).
  • the density of Co is locally high, and not only the Fe at the same site as Co but also the density of La and Sr at another site is low at that location.
  • region (a) contains Co 3 -x Fe x O 4- ⁇ (e.g., Co 3 O 4) is, La 2-x Sr in the area (b) x Co 1-y Fe y O 4- ⁇ ( e.g., La 1.2 Sr 0. 8 Co 0.5 Fe 0.5 O 4- ⁇ ).
  • La, Sr, Co, and Fe are relatively uniformly distributed in the oxygen electrode 15.
  • This current density is measured in the EC mode and the same cell voltage.
  • the current density in the initial state of Example 1-3 is an equivalent value and is in good agreement.
  • the current density in the initial state of the comparative example is lower than the values of Examples 1 to 3. Further, the deterioration rate of the comparative example was larger than the deterioration rate of Example 3.
  • This result relates to the presence of a plurality of phases coexisting in the oxygen electrode 15, for example, the existence of “regions where the density of Co is high and the density of Fe, La, and Sr is low” (second phase). Conceivable.
  • the presence of the second phase 152 improves the initial characteristics and also improves the life (deterioration rate).
  • the uniform oxygen electrode 15 as in the comparative example is considered to be in a more stable state and have a longer lifetime, but the embodiment in which the phases are not uniform has a longer lifetime.
  • the presence of a plurality of phases is considered to contribute to the performance and stabilization of the oxygen electrode.
  • the performance of the oxygen electrode can be improved.

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Abstract

La cellule électrochimique selon un mode de réalisation de la présente invention comprend : un premier oxyde ayant une structure pérovskite, ledit premier oxyde étant disposé dans une région prédéterminée; et un second oxyde, qui est disposé en étant dispersé dans la région prédéterminée, et qui a un élément constitutif à une densité qui est supérieure à celle du premier élément constitutif dans le premier oxyde.
PCT/JP2017/010500 2017-03-15 2017-03-15 Électrode à oxygène pour cellule électrochimique, et cellule électrochimique Ceased WO2018167889A1 (fr)

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JP2019505599A JP6833974B2 (ja) 2017-03-15 2017-03-15 電気化学セル用酸素極および電気化学セル

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020123566A (ja) * 2019-01-30 2020-08-13 日本碍子株式会社 電気化学セル
US11682771B2 (en) 2020-07-02 2023-06-20 Toshiba Energy Systems & Solutions Corporation Electrochemical cell and electrochemical cell stack

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06279144A (ja) * 1993-03-29 1994-10-04 Ngk Insulators Ltd 多孔質焼結体の製造方法
JPH06279141A (ja) * 1993-03-29 1994-10-04 Ngk Insulators Ltd 多孔質焼結体の製造方法
JP2011228271A (ja) * 2010-03-31 2011-11-10 Toto Ltd 空気極材料および固体酸化物形燃料電池
JP2014089816A (ja) * 2012-10-29 2014-05-15 Toshiba Corp 電気化学セル及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06279144A (ja) * 1993-03-29 1994-10-04 Ngk Insulators Ltd 多孔質焼結体の製造方法
JPH06279141A (ja) * 1993-03-29 1994-10-04 Ngk Insulators Ltd 多孔質焼結体の製造方法
JP2011228271A (ja) * 2010-03-31 2011-11-10 Toto Ltd 空気極材料および固体酸化物形燃料電池
JP2014089816A (ja) * 2012-10-29 2014-05-15 Toshiba Corp 電気化学セル及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020123566A (ja) * 2019-01-30 2020-08-13 日本碍子株式会社 電気化学セル
US11682771B2 (en) 2020-07-02 2023-06-20 Toshiba Energy Systems & Solutions Corporation Electrochemical cell and electrochemical cell stack

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