WO2017155188A1 - Pile à combustible à oxyde solide et son procédé de fabrication - Google Patents

Pile à combustible à oxyde solide et son procédé de fabrication Download PDF

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WO2017155188A1
WO2017155188A1 PCT/KR2016/014686 KR2016014686W WO2017155188A1 WO 2017155188 A1 WO2017155188 A1 WO 2017155188A1 KR 2016014686 W KR2016014686 W KR 2016014686W WO 2017155188 A1 WO2017155188 A1 WO 2017155188A1
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layer
electrolyte
fuel cell
reaction prevention
prevention layer
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PCT/KR2016/014686
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English (en)
Korean (ko)
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배홍열
안진수
박영민
배원수
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재단법인 포항산업과학연구원
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Publication of WO2017155188A1 publication Critical patent/WO2017155188A1/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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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
    • 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
    • H01M8/1253—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 the electrolyte containing zirconium oxide
    • 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
    • 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 solid oxide fuel cell (SOFC), and more particularly, to a solid oxide fuel cell including a reaction preventing layer between an electrolyte and a fuel electrode.
  • SOFC solid oxide fuel cell
  • a fuel cell is a device that generates electricity by reacting fuel such as hydrogen or natural gas with oxygen, and is recognized as one of the main energy technologies of the future because of its high efficiency, pollution-free, and noise-free characteristics.
  • Solid Oxide Fuel Cells use solid oxides as electrolytes to pass oxygen ions.
  • the electrolyte materials include zirconia (ZrO 2 ) oxides, ceria (CeO 2 ) oxides, and lanthanum-strontium-gadolinium.
  • Magnesium oxide (LSGM) or the like is used.
  • the electrolyte is yttria (Y 2 O 3 ), ceria (CeO 2 ), scandia (Sc 2 O 3 ), gadolinium oxide (Gd 2 O 3 ) and the like for the purpose of improving thermal stability and ionic conductivity at high temperature. Contains some stabilizer.
  • the unit cell of a solid oxide fuel cell has the solid electrolyte described above, and is formed in such a manner that an air electrode is attached to one side and a fuel electrode is attached to the other side.
  • SOFC solid oxide fuel cell
  • a conventional anode a mixture of nickel oxide (NiO) and yttrium stabilized zirconia (YSZ) is used.
  • NiO nickel oxide
  • YSZ yttrium stabilized zirconia
  • LSC Lanthanum-strontium-cobalt oxide
  • LSM lanthanum-strontium-manganese oxide
  • LSCF lanthanum-strontium- Cobalt-iron oxide
  • BSCF barium-strontium-cobalt-iron oxide
  • LSCF lanthanum-strontium-cobalt-iron oxide
  • BSCF barium-strontium-cobalt-iron oxide
  • Air cathodes are used a lot.
  • the lanthanum-strontium-cobalt-iron oxide (LSCF) -based or barium-strontium-cobalt-iron oxide (BSCF) -based cathode material has a property of reacting with a zirconia (ZrO 2 ) -based electrolyte, thereby sintering the cathode.
  • ZrO 2 zirconia
  • complex ions with low ion conductivity such as lanthanum zirconate (La 2 Zr 2 O 7 ) or strontium zirconate (SrZrO 3 ), are formed at the interface between the cathode and the electrolyte .
  • reaction compound as described above decreases the rate at which oxygen ions formed in the cathode diffuse through the electrolyte and react with hydrogen in the anode, thereby degrading the overall performance of the fuel cell and causing thermal and mechanical stability by causing a difference in thermal expansion coefficient. This causes a decrease.
  • a reaction preventing layer is introduced between the two.
  • a ceria-based oxide doped with gadolinium (Gd), samarium (Sm), or yttrium (Y) is typically used.
  • the method for producing the reaction prevention layer can be largely divided into a high temperature process method and a low temperature process method.
  • the high temperature process method there is a method such as applying a sintered ceria doped with Gd or the like by screen printing method or the like and sintering as in Patent Document 1. Since the ceria-based material is poor in sintering property, if the sintering is not performed at a high temperature, the density of the ceria-based material may not be able to act as a reaction prevention layer, and the bonding strength may be reduced to peel off from the electrolyte.
  • the low temperature process method does not go through the high temperature process in the cell manufacturing process of the reaction prevention layer formation and the cathode formation. Specifically, the whole process of manufacturing a cell is performed at 1100 degrees C or less.
  • the reaction prevention layer is formed by a low temperature process
  • a chemical reaction between the ceria-based reaction prevention layer and the Zirkorea electrolyte layer generated at a high temperature can be prevented, and thus phase generation can be suppressed. Therefore, since the cell produced by the low temperature process method has a small activation energy of the electric conductivity according to the temperature, the cell produced by the low temperature process exhibits excellent performance in the medium and low temperature regions because the decrease in the electric conductivity according to the temperature is alleviated.
  • said low temperature process method there exist methods, such as a pulse laser, aerosol vapor deposition (patent document 2), sputtering, an electron beam vapor deposition.
  • the interface portion between the zirconia-based electrolyte and the ceria-based reaction prevention layer is very sensitive to various process conditions.
  • thermal, mechanical, and electrical inconsistencies at the interface between two materials increase the electrical resistance of the cell, weaken the bonding strength, and cause delamination of the intercalation, or the loose strontium (Sr) contained in the cathode layer.
  • diffusion causes a problem such as generation of a high resistance strontium zirconia (SrZrO 3 ) phase, causing variation in cell performance, thereby making it difficult to secure stable cell performance.
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2015-0123527
  • Patent Document 2 Korean Unexamined Patent Publication No. 10-2013-0065221
  • One aspect of the present invention is to provide a solid oxide fuel cell and a method of manufacturing the same, which has excellent performance even in the mid- and low temperature range and can secure stable cell performance by minimizing deviation.
  • the present invention includes a fuel electrode, an electrolyte and an air electrode,
  • reaction prevention layer formed between the electrolyte and the air electrode
  • It provides a solid oxide fuel cell comprising a relaxation layer formed between the electrolyte and the reaction prevention layer.
  • the present invention comprises the steps of preparing a half cell formed with the anode and the electrolyte;
  • It provides a method for producing a solid oxide fuel cell comprising the step of forming an air electrode on the reaction prevention layer.
  • the reaction prevention layer is formed between the electrolyte and the cathode by using a low temperature process, the chemical reaction between the ceria-based reaction prevention layer and the zirconia-based electrolyte layer generated at a high temperature can be prevented. Through this, not only excellent output performance can be secured, but also reduction of electrical conductivity can be alleviated, thereby ensuring excellent electrical performance in the mid- and low temperature regions.
  • 1 is a graph evaluating the performance of a fuel cell in which a reaction prevention layer is manufactured by a high temperature process method and a low temperature process method.
  • FIG. 2 is a photograph of observing and analyzing a phase formed at an interface between the reaction prevention layer and the electrolyte layer in a fuel cell in which the reaction prevention layer is manufactured by a low temperature process method.
  • FIG. 3 is a graph evaluating the performance of a fuel cell in which a reaction prevention layer is manufactured by a low temperature process method.
  • FIG. 4 is a schematic view showing a fuel cell of the present invention.
  • FIG. 6 is a graph evaluating the performance of a fuel cell in which a relaxed layer of the present invention is formed.
  • the solid oxide fuel cell of the present invention includes a fuel electrode 10, an electrolyte 20, and an air electrode 30, and a reaction preventing layer 40 is formed between the electrolyte 20 and the air electrode 30.
  • a relaxation layer 50 is formed between the electrolyte 20 and the reaction prevention layer 40.
  • a solid oxide fuel cell generally has an electrolyte 20 in the center, and a fuel electrode 10 and an air electrode 30 on both sides of the electrolyte.
  • oxygen receives electrons and becomes oxygen ions and passes through the electrolyte 20.
  • oxygen ions release electrons and react with hydrogen gas. Water vapor is formed.
  • the electrolyte 20 of the solid oxide fuel cell should not be permeable due to its compactness, and should not have electron conductivity but high oxygen ion conductivity, and the electrode should be porous to allow gas to diffuse well and have high electron conductivity. .
  • the anode 10 may be divided into an anode support layer 11 and an anode functional layer 12.
  • the anode support layer 11 and the anode functional layer 12 may be formed of a composite of nickel and stabilized zirconia. It is preferable to have a porous structure for smooth fuel gas flow.
  • the electrolyte uses an ion conductive solid oxide, and specifically, zirconia (ZrO 2 ) -based oxide, ceria (CeO 2 ) -based oxide, lanthanum-strontium-gadolinium-magnesium oxide (LSGM), and the like may be used.
  • zirconia-based oxides are preferable, and as an example, yttrium stabilized zirconia (YSZ), scandium stabilized zirconia (ScSZ) and the like can be used.
  • YSZ yttrium stabilized zirconia
  • ScSZ scandium stabilized zirconia
  • at least one of yttrium (Y) and scandium (Sc) is zirconia included in the range of 1 at.% To 40 at.%.
  • the concentration of oxygen vacancies is too low, leading to a decrease in the oxygen ion conductivity and the electrical conductivity of the electrolyte material.
  • it exceeds 40at.% The oxygen ion mobility may be lowered due to the incorporation of oxygen vacancies, which may cause a decrease in oxygen ion conductivity and electrical conductivity of the electrolyte material.
  • the cathode may be lanthanum-strontium-manganese oxide (LSM), lanthanum-strontium-cobalt oxide (LSC), lanthanum-strontium-cobalt-iron oxide (LSCF), barium-strontium-cobalt-iron oxide (BSCF), or the like.
  • Lanthanum-strontium-cobalt-iron oxide (LSCF) may be preferably used.
  • the lanthanum-stromium-cobalt-iron oxide (LSCF) used as the cathode material may be used alone, or may be mixed with zirconia or ceria-based oxide.
  • the reaction prevention layer serves to prevent the material constituting the cathode (eg, LSCF) from reacting with zirconium (Zr) constituting the electrolyte.
  • the reaction layer is a sintered cathode to produce a solid oxide fuel cell, or the zirconium of the electrolyte reacts with the material constituting the cathode while the battery is operating at a high temperature, lanthanum zirconia (La 2 Zr 2 O 7 ) or strontium zirconia (SrZrO 3 ) to inhibit high resistance phase generation.
  • the high resistance phase such as lanthanum zirconia (La 2 Zr 2 O 7 ) or strontium zirconia (SrZrO 3 ), reduces the rate at which oxygen ions generated in the anode diffuse through the electrolyte and react with hydrogen in the cathode. By lowering, it becomes a cause of reducing overall fuel cell performance.
  • the material used for the reaction prevention layer is preferably ceria-based oxide, and more preferably doped ceria (GDC) doped with gadolinium (Gd), ceria (SDC) doped with samarium (Sm), or yttrium (Y) doped.
  • GDC doped ceria
  • SDC ceria
  • Y ceria
  • La lanthanum
  • LDC lanthanum doped ceria
  • at least one of the gadolinium (Gd), samarium (Sm), yttrium (Y), and lanthanum (La) is included in the range of 1at.% To 40at.%.
  • the concentration of oxygen vacancies is too low to reduce the oxygen ion conductivity and the electrical conductivity of the reaction prevention layer material.
  • the oxygen ion mobility may be lowered due to the incorporation of oxygen vacancies, which may cause a decrease in oxygen ion conductivity and electrical conductivity of the reaction prevention layer material.
  • the reaction prevention layer is preferably formed in a pore-free structure, the pores may be locally formed according to the process conditions, in this case it is preferable that the pore size has a size of 0.1 ⁇ m or less.
  • the thickness of the reaction prevention layer is preferably 0.1 ⁇ 2.0 ⁇ m.
  • the thickness of the reaction prevention layer is less than 0.1 ⁇ m, not only the formation of the film quality is difficult, but also the thickness of the film may be uneven during film formation, so that the reaction between the cathode and the electrolyte may occur locally.
  • the thickness is more than 2 ⁇ m can effectively prevent the reaction between the electrolyte and the cathode, in this case, since the reaction prevention layer itself acts as a resistance, it is preferable not to exceed 2 ⁇ m.
  • the mitigating layer 50 constituting the fuel cell of the present invention is positioned between the two layers to resolve structural inconsistency between the electrolyte and the reaction preventing layer, inconsistency of the thermal expansion coefficient, and the like. That is, the relaxation layer serves to alleviate the sudden change in the lattice constant and crystal structure of the electrolyte and the reaction prevention layer, not only improves the bonding strength between the two layers, but also serves to reduce the difference in the coefficient of thermal expansion thermally, It has structural robustness against mechanical change. As a result, there is a technical significance to secure stable battery performance.
  • the alleviation layer may be composed of a composite of an electrolyte material (M) and a reaction prevention layer material (N).
  • the relaxation layer preferably has an electrolyte material and a reaction prevention layer in an atomic ratio (atomic%, M: N) of 1: 9-9: 1. If the atomic ratio between the materials is out of the above range, the amount of one of the two materials is so insufficient that it is difficult to form a composite, whereby the structural mismatch using the composite and the relaxation of the mismatch of the thermal expansion coefficient cannot be secured.
  • the electrolyte material (M) is a zirconia-based oxide electrolyte material, it may be represented by A x Zr 1-x O 2- ⁇ , wherein A is at least one of yttrium (Y), scandium (Sc) And x may range from 0.01 to 0.4.
  • the reaction layer material (N) is a ceria-based oxide, may be represented by B y Ce 1-y O 2- ⁇ , wherein B is gadolinium (Gd), samarium (Sm), yttrium (Y), lanthanum (La) may be one or more, and y may have a range of 0.01 to 0.4.
  • ⁇ means the concentration of oxygen vacancies (site where oxygen is missing in the lattice). For example, when Z is added to ZrO 2 , the corresponding oxygen is released (if two Y are added, one oxygen is released to create an empty spot. However, the concentration of the vacancies also depends on other factors such as oxygen partial pressure. It is not represented by x / 2 because it is affected, and is usually expressed mainly by 2- ⁇ ).
  • the thickness of the relaxation layer is about 10 to 30% of the thickness of the reaction prevention layer. That is, since the thickness of the reaction prevention layer has a range of 0.1 ⁇ 2.0 ⁇ m, it is preferable that the thickness of the relaxation layer is 0.01 ⁇ 0.6 ⁇ m.
  • the thickness of the alleviation layer is too thin, it is difficult to secure the structural mismatch, the thermal expansion coefficient mismatch relaxation effect, while if too thick, the electrical resistance of the alleviation layer itself increases, causing a decrease in cell performance.
  • the alleviation layer and the reaction prevention layer is preferably manufactured using a low temperature process method.
  • a low temperature process method there are pulse laser deposition, aerosol deposition, sputtering deposition, electron beam deposition, and the like.
  • the heat treatment may be performed to manufacture a fuel cell after heating or deposition during the deposition process, but the temperature does not exceed 1100 ° C. is referred to as a low temperature process method.
  • the high temperature process method over 1100 ° C.
  • zirconium (Zr) in the electrolyte and the cerium (Ce) of the relaxation layer or the reaction prevention layer react with each other at a high temperature, and thus high resistance cerium Phases of zirconia (Ce 2 Zr a O 7 + x ) are formed, resulting in increased battery resistance due to increased resistance.
  • the low temperature process method for forming the alleviation layer and the reaction prevention layer may use different methods, but it is advantageous to perform the same method in terms of simplifying the process and reducing the cost.
  • the electron beam deposition method which has a fast deposition rate even at low temperature in the low temperature process method, and can also deposit on a large range of large area substrate using a small target.
  • Preferred manufacturing method in the present invention comprises the steps of preparing a half cell formed with the anode and the electrolyte; Forming a relaxation layer on the electrolyte of the half cell using a low temperature process method; Forming a reaction prevention layer on the alleviation layer by using a low temperature process method; And forming an air electrode on the reaction prevention layer.
  • the method for forming the anode and the electrolyte is not particularly limited in the present invention, and a half cell is manufactured by a conventional method performed in the technical field to which the present invention belongs. As a preferable example, a tape casting method or the like can be used.
  • a mixture of nickel oxide (NiO) and zirconia (ZrO 2 ) may be formed by a tape casting method, and the electrolyte layer may be formed by casting a material such as yttria stabilized zirconia (YSZ). It can form using a method.
  • NiO nickel oxide
  • ZrO 2 zirconia
  • YSZ yttria stabilized zirconia
  • a sintering heat treatment may be performed to manufacture a half cell.
  • a relaxation layer is formed on the prepared electrolyte of the half cell, and a reaction prevention layer is formed on the relaxation layer.
  • the low temperature process includes pulse laser deposition, aerosol deposition, sputtering deposition, electron beam deposition, and the like.
  • the electron beam deposition method which has a fast deposition rate even at low temperature, and can also deposit on a large range of large area substrate using a small target.
  • the relaxation layer and the reaction prevention layer are sequentially formed by an electron beam deposition method, but no additional heat treatment is performed. This is because the heat treatment is included in the formation of the air electrode in the future.
  • heat treatment may be performed during the relaxation layer formation process or the reaction prevention layer formation process.
  • the heat treatment at this time is preferably not more than 1100 °C. If the heat treatment temperature exceeds 1100 °C, as mentioned earlier, the formation of a high-resistance phase of cerium zirconia (Ce 2 Zr a O 7 + x ) to increase the resistance causes the battery performance degradation .
  • the cathode material may be LSCF, or the like, and may be used in combination with zirconia or ceria oxide as well as single use.
  • the method for forming the air electrode is not particularly limited in the present invention, and is based on a conventional method performed in the technical field to which the present invention belongs.
  • the cathode material is coated by screen printing, and heat treatment is performed at a temperature in the range of 800 to 1100 ° C.
  • the reference example is a result of analyzing the performance for each operation temperature between the cell formed the reaction layer in the high temperature process and the cell formed the reaction layer in the low temperature process in forming the reaction layer between the electrolyte and the cathode.
  • anode fuel electrode support and anode functional layer
  • NiO nickel oxide
  • ZrO 2 zirconia
  • the electrolyte was formed by yttria stabilized zirconia (YSZ) by tape casting, followed by sintering to prepare a half cell.
  • Gd-doped ceria (GDC) oxide was coated by screen printing, which is a high temperature process, and sintered by heat treatment at 1250 ° C.
  • the low temperature process was deposited at 100 ° C. by an electron beam deposition method, and no additional heat treatment was performed.
  • the cathode material mixed with LSCF and GDC is coated by screen printing, and sintered and heat treated at 1000 ° C. to finally manufacture the fuel cell manufactured by the high temperature process method and the fuel cell manufactured by the low temperature process method, respectively. It was.
  • the comparative example is a result of analyzing the reaction prevention layer and the electrolyte of the fuel cell in which the reaction prevention layer is manufactured by the low temperature process method based on the reference example, and manufacturing a plurality of fuel cells and evaluating the same.
  • a reaction prevention layer was formed on the half cell formed by the same method as the reference example by using an electron beam deposition method at 100 ° C. using a target made of GDC oxide on the electrolyte of the half cell. Thereafter, the cathode material in which the LSCF and GDC were mixed was applied by screen printing, and the fuel cell was manufactured by sintering heat treatment at 1000 ° C. Six fuel cells were fabricated in the same manner six times.
  • the GDC oxide was a material containing 20 at.% Of GD, and the deposition thickness was about 0.3 to 0.4 ⁇ m.
  • FIG. 2 With the fuel cell sample fabricated for the third time in the sixth manufacturing process, the cross section was observed and the result is shown in FIG. 2. As shown in Figure 2 (a), it was confirmed that a high resistance strontium zirconia phase was formed along the interface between the reaction prevention layer and the electrolyte. In particular, when the component is analyzed in FIG. 2 (b), it can be seen that the components of the reaction prevention layer and the electrolyte layer interface are mainly oxides of Sr and Zr.
  • a half cell was prepared in the same manner as the reference example and the comparative example. Subsequently, on the electrolyte of the half cell, the target was formed of a composite of GDC and YSZ, and was deposited at 100 ° C. by electron beam deposition to form a relaxed layer. At this time, the GDC oxide was a material containing 20at.% Of Gd, and YSZ was a material containing 16at.% Of Y. Meanwhile, the atomic ratio between the GDC and YSZ was maintained at 5: 5, and the relaxed layer formed had a thickness of about 0.05 ⁇ m. No additional heat treatment was performed during the relaxation layer formation.
  • the relaxation layer was formed, it was deposited at 100 ° C. by an electron beam deposition method using a target made of GDC oxide to form a reaction prevention layer.
  • the GDC oxide was a material containing 20at.% Gd. No additional heat treatment was performed during the reaction prevention layer formation process.
  • the thickness of the reaction prevention layer was formed to a thickness of about 0.3 ⁇ 0.4 ⁇ m.
  • the cathode material in which the LSCF and GDC were mixed was applied by screen printing, and the fuel cell was manufactured by sintering heat treatment at 1000 ° C. Six fuel cells were fabricated in the same manner six times.
  • FIG. 5 After manufacturing six fuel cells having the form of FIG. 4 by the above method, the reaction between the reaction layer and the electrolyte of the first fuel cell was analyzed and the results are shown in FIG. 5.
  • FIG. 5 (a) it can be seen that a relaxation layer is formed between the reaction prevention layer and the electrolyte.
  • FIG. 5 (b) Ce and Zr are observed as main materials of the relaxation layer.
  • FIG. 6 the performance deviation of the six fuel cells is analyzed and the results are shown in FIG. 6.
  • the result of FIG. 6 is the same as that of FIG. 3.
  • a fuel cell in which a mitigating layer and a reaction prevention layer are formed shows very stable cell performance regardless of manufacturing order. That is, it can be seen that the performance of the battery is very robust against the micro fluctuation factor of the process.

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Abstract

La présente invention concerne une pile à combustible à oxyde solide (SOFC) et, plus spécifiquement, une SOFC comprenant une couche de prévention de réaction entre un électrolyte et une anode.
PCT/KR2016/014686 2016-03-11 2016-12-15 Pile à combustible à oxyde solide et son procédé de fabrication WO2017155188A1 (fr)

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CN116914173A (zh) * 2023-09-05 2023-10-20 中石油深圳新能源研究院有限公司 致密隔离层及其制备方法、固态氧化物燃料电池

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KR102229377B1 (ko) * 2019-02-01 2021-03-18 한양대학교 산학협력단 고체산화물 연료전지 및 이의 제조방법
JP7091278B2 (ja) * 2019-03-29 2022-06-27 株式会社豊田中央研究所 固体酸化物型燃料電池用電極材料、それを用いた固体酸化物型燃料電池用アノード電極、及びそれを用いた固体酸化物型燃料電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2398103A1 (fr) * 2010-06-15 2011-12-21 NGK Insulators, Ltd. Pile à combustible
KR20120074790A (ko) * 2010-12-28 2012-07-06 주식회사 포스코 고체산화물 연료전지 및 그 제조 방법
US20120225368A1 (en) * 2011-03-03 2012-09-06 Ngk Insulators, Ltd. Solid oxide fuel cell
KR20120140476A (ko) * 2011-06-21 2012-12-31 삼성전자주식회사 고체산화물 연료전지용 소재, 상기 소재를 포함하는 캐소드 및 상기 소재를 포함하는 고체산화물 연료전지
KR20150123527A (ko) * 2014-04-25 2015-11-04 한국과학기술연구원 반응방지막을 포함하는 고온 고체산화물 셀, 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2398103A1 (fr) * 2010-06-15 2011-12-21 NGK Insulators, Ltd. Pile à combustible
KR20120074790A (ko) * 2010-12-28 2012-07-06 주식회사 포스코 고체산화물 연료전지 및 그 제조 방법
US20120225368A1 (en) * 2011-03-03 2012-09-06 Ngk Insulators, Ltd. Solid oxide fuel cell
KR20120140476A (ko) * 2011-06-21 2012-12-31 삼성전자주식회사 고체산화물 연료전지용 소재, 상기 소재를 포함하는 캐소드 및 상기 소재를 포함하는 고체산화물 연료전지
KR20150123527A (ko) * 2014-04-25 2015-11-04 한국과학기술연구원 반응방지막을 포함하는 고온 고체산화물 셀, 이의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116914173A (zh) * 2023-09-05 2023-10-20 中石油深圳新能源研究院有限公司 致密隔离层及其制备方法、固态氧化物燃料电池
CN116914173B (zh) * 2023-09-05 2023-11-24 中石油深圳新能源研究院有限公司 致密隔离层及其制备方法、固态氧化物燃料电池

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