WO2013173981A1 - Anode-supported solid oxide fuel cell and method for preparing same - Google Patents

Anode-supported solid oxide fuel cell and method for preparing same Download PDF

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WO2013173981A1
WO2013173981A1 PCT/CN2012/075915 CN2012075915W WO2013173981A1 WO 2013173981 A1 WO2013173981 A1 WO 2013173981A1 CN 2012075915 W CN2012075915 W CN 2012075915W WO 2013173981 A1 WO2013173981 A1 WO 2013173981A1
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anode
layer
fuel cell
side electrolyte
solid oxide
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PCT/CN2012/075915
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French (fr)
Chinese (zh)
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杨绍华
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Yang Shaohua
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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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • 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
    • 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
    • H01M8/126—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 cerium 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 invention relates to the technical field of fuel cell materials, in particular to an anode supported solid oxide fuel cell and a preparation method thereof.
  • a solid oxide fuel cell is a highly efficient all-solid-state electrochemical energy conversion device that directly converts chemical energy into electrical energy, and its loss is mainly concentrated on the internal resistance loss of the electrolyte material.
  • the existing Chinese Patent Publication No. CN100479245C discloses a medium-temperature solid oxide fuel cell anode-supported solid electrolyte composite membrane and a preparation method thereof, the composite membrane is composed of a nickel oxide-yttria-stabilized zirconia composite cermet anode and a weight ratio of 6 to 10% yttria-stabilized zirconia (YSZ) or yttria-stabilized zirconia (SSZ) or yttria-doped yttria (CGO) electrolyte layer consisting of two layers, cast by casting, composite membrane area 100 ⁇ 100 (mm) 2 or more, the electrolyte thickness is 10 to 30 ⁇ m, and the anode thickness is 0.5 to 1.5 mm.
  • the anode is made of NiO+ (6-10%) mol
  • the YSZ is composed of an electrolyte composed of one of 8YSZ, SSZ or CGO.
  • the composite film is flat and meets the requirements for use, it has the following disadvantages: (1) 8YSZ is used as an electrolyte, the ionic conductivity is too low, and the product power density is low.
  • the cathode material easily reacts with ZrO 2 (zirconia) in the electrolyte to affect the power of the battery; (2) the CGO material has high conductivity, but is easily affected by the reduction of the anode fuel gas, affecting reliability; (3) the conductivity of the SSZ ion is high, However, the cost is high, and Sc ( ⁇ ) is in the natural world and its scarcity, the supply cannot keep up, and mass production cannot be formed; (4) NiO+(6 ⁇ 10)%mol YSZ material has low strength, and the support will affect the reliability.
  • the present invention provides an anode-supported solid oxide fuel cell, which effectively improves the power density of the single cell through material and structure design, improves the mechanical strength and reliability of the product, reduces the production cost, and is suitable for batch production. Production.
  • the invention also provides a preparation method of an anode-supported solid oxide fuel cell, which can effectively reduce the thickness of the electrolyte and ensure the compactness of the electrolyte by the thin layer casting process.
  • the technical solution adopted by the present invention is:
  • An anode-supported solid oxide fuel cell characterized by: sequentially comprising an anode support layer, an anode functional layer, a fuel side electrolyte layer, an air side electrolyte layer and a cathode layer;
  • the composition of the anode supporting layer is NiO+YSZ, wherein YSZ is 2-6 mol% yttria-stabilized zirconia, and the composition of the anode functional layer is NiO+YSZ, wherein YSZ is 5-12 mol% yttria stable
  • the zirconia, the composition of the fuel-side electrolyte layer is 5 to 12 mol% of yttria-stabilized zirconia, and the composition of the air-side electrolyte layer is ruthenium oxide or rare earth-doped ruthenium oxide.
  • NiO nickel oxide + 2 ⁇ 6YSZ (2 ⁇ 6mol% yttrium stabilized zirconia) is used as the anode support layer material, which effectively improves the strength of the support and the single cell;
  • NiO nickel oxide + 5 ⁇ 12YSZ (5 ⁇ 12mol% yttrium stabilized zirconia) is used as the anode functional layer material, which effectively improves the performance of the three-phase interface and reduces the polarization resistance of the single cell;
  • 5 to 12YSZ (5 to 12 mol% of yttria-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 are used as the dual electrolyte material, and 5 to 12 YSZ (5 to 12 mol% of yttrium-stabilized zirconia) is placed close to the anode side.
  • 5 to 12 YSZ (5 to 12 mol% of yttrium-stabilized zirconia) is placed close to the anode side.
  • CeO 2 (yttria) or rare earth doped CeO 2 close to the cathode side (air side), effectively preventing the cathode from reacting with ZrO 2 (zirconia), and effectively preventing fuel gas and CeO 2 ( The reaction of cerium oxide or rare earth doped CeO 2 .
  • the cathode layer is one or more of cerium manganese, samarium cobalt iron, samarium cobalt, samarium cobalt iron, strontium nickel iron and samarium cobalt iron samarium.
  • the anode support layer has a thickness of 0.1 to 1.0 mm
  • the anode functional layer has a thickness of 5 to 30 ⁇ m
  • the fuel side electrolyte layer has a thickness of 0.5 to 15 ⁇ m
  • the air side electrolyte layer has a thickness of 0.5 to 15 ⁇ m.
  • the cathode material is made into a printing paste, printed on the air-side electrolyte layer, and the cathode is sintered in the furnace.
  • the anode-supported solid oxide fuel cell of the present invention uses 5 to 12YSZ (5 to 12 mol% of yttrium-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 as a dual electrolyte material, and 5 to 12YSZ (5 to 5 12 mol% yttrium stabilized zirconia) close to the anode side (fuel side), CeO 2 (yttria) or rare earth doped CeO 2 close to the cathode side (air side), effectively preventing the cathode from reacting with ZrO 2 (zirconia), Effectively preventing the reaction of the fuel gas with CeO 2 (cerium oxide) or rare earth doped CeO 2 , greatly improving the reliability of the anode supported solid oxide fuel cell;
  • NiO (nickel oxide) + 2 ⁇ 6YSZ (2 ⁇ 6mol% yttria stabilized zirconia) as anode support layer material
  • 5 to 12YSZ (5 to 12 mol% of yttrium-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 can be suitably used for mass production.
  • the preparation method of the anode-supported solid oxide fuel cell of the invention adopts a low-cost casting process capable of mass production to fabricate an anode support layer, an anode functional layer and an electrolyte layer, and a cathode layer is formed by a printing process, which is effective by a thin layer casting process.
  • the thickness of the electrolyte layer (0.5 to 15 ⁇ m) and use high-ion-conducting CeO 2 (yttria) or rare earth doped CeO 2 as the electrolyte material to improve the conductivity of the electrolyte ions; use NiO (nickel oxide) + 5 ⁇ 12YSZ (5 ⁇ 12mol% yttrium-stabilized zirconia) is used as the anode functional layer material, and the anode support layer, the anode functional layer and the double electrolyte layer green sheets are laminated and integrated together, thereby effectively improving the performance of the anode-electrolyte interface.
  • Figure 1 is a cross-sectional view showing an anode supported solid oxide fuel cell of the present invention.
  • the anode supported solid oxide fuel cell is sequentially composed of an anode supporting layer 1, an anode functional layer 2, a fuel side electrolyte layer 3, and an air side electrolyte layer 4. And the cathode layer 5 is composed.
  • the anode support layer 1 ceramic slurry was prepared separately, and its composition was 1:1 5YSZ (5mol% yttrium stabilized zirconia) + NiO (nickel oxide); anode functional layer 2 ceramic slurry, its composition was 1:1 10YSZ (10 mol% yttrium stabilized zirconia) + NiO (nickel oxide); fuel side electrolyte layer 3 ceramic slurry, the composition of which is 10YSZ (10 mol% yttrium stabilized zirconia); air side electrolyte layer 4 ceramic slurry, the composition of which is GOC (gallium doped yttrium oxide);
  • an anode support layer 1 ceramic film tape, an anode functional layer 2 ceramic film tape, a fuel side electrolyte layer 3 ceramic film tape, and an air side electrolyte layer 4 ceramic film tape are prepared by a casting method;
  • the anode support layer 1 ceramic film tape, the anode functional layer 2 ceramic film tape, the fuel side electrolyte layer 3 ceramic film tape, and the air side electrolyte layer 4 ceramic film tape are sequentially laminated and pressed, and then sintered on the air side electrolyte.
  • the LSCF (samarium cobalt iron) cathode layer 5 is printed on the layer, and finally cathode sintering is performed.
  • An anode-supported solid oxide fuel cell is obtained by the above preparation method, and the anode support layer 1 has a thickness of 0.5 In mm, the anode functional layer 2 has a thickness of 15 ⁇ m, the fuel-side electrolyte layer 3 has a thickness of 10 ⁇ m, and the air-side electrolyte layer 4 has a thickness of 10 ⁇ m.
  • the power density of the battery at 800 ° C was measured: 0.45 W/cm 2 , 1000 hr attenuation: 0.31%.
  • the anode-supported solid oxide fuel cell prepared by the method for preparing the anode-supported solid oxide fuel cell of the present embodiment effectively improves the power density of the single cell and the mechanical strength of the product through the design of materials and structures, and has good electrical conductivity and reliability. High, low cost, suitable for mass production; through the thin layer casting process, it not only effectively reduces the thickness of the electrolyte, but also ensures the compactness of the electrolyte.

Abstract

The present invention relates to the technical field of fuel cell materials, and in particular, to an anode-supported solid oxide fuel cell, consisting of an anode supporting layer, an anode functional layer, a fuel side electrolyte layer, an air side electrolyte layer and a cathode layer in sequence. NiO+YSZ is used as the material of the anode supporting layer, the NiO+YSZ is used as the material of the anode functional layer, and YSZ and CeO2 or rare-earth-doped CeO2 are used as the materials of two electrolytes. The present invention further provides a method for preparing an anode-supported solid oxide fuel cell. For an anode-supported solid oxide fuel cell prepared by using the method for preparing an anode-supported solid oxide fuel cell, the power density of a single cell and the mechanical strength of the product are effectively improved through material and structural design, and the anode-supported solid oxide fuel cell has a good electric conductivity, high reliability and low cost and is suitable for batch production; and by means of a thin layer casting process, not only the thickness of the electrolytes is reduced effectively, but also the compactness of the electrolytes is guaranteed.

Description

一种阳极支撑固体氧化物燃料电池及其制备方法Anode supported solid oxide fuel cell and preparation method thereof
技术领域 Technical field
本发明涉及燃料电池材料技术领域，尤涉及一种阳极支撑固体氧化物燃料电池及其制备方法。 The invention relates to the technical field of fuel cell materials, in particular to an anode supported solid oxide fuel cell and a preparation method thereof.
背景技术 Background technique
固体氧化物燃料电池是将化学能直接转化为电能的高效全固态电化学能转换装置，其损耗主要集中在电解质材料的内阻损耗。 A solid oxide fuel cell is a highly efficient all-solid-state electrochemical energy conversion device that directly converts chemical energy into electrical energy, and its loss is mainly concentrated on the internal resistance loss of the electrolyte material.
现有中国专利公告号为CN100479245C公开了一种中温固体氧化物燃料电池阳极支撑固体电解质复合膜及其制备方法，该复合膜由氧化镍-氧化钇稳定的氧化锆复合金属陶瓷阳极和重量比为6～10%氧化钇稳定的氧化锆（YSZ）或氧化钪稳定的氧化锆（SSZ）或掺杂氧化钆的氧化铈（CGO）电解质层两层组成，通过流延制成，复合膜面积100×100（mm） ² 以上，电解质厚度10～30μm，阳极厚度0.5～1.5mm。优选阳极由NiO+(6～10)%mol YSZ构成，电解质由8YSZ、SSZ或CGO中的一种构成。 The existing Chinese Patent Publication No. CN100479245C discloses a medium-temperature solid oxide fuel cell anode-supported solid electrolyte composite membrane and a preparation method thereof, the composite membrane is composed of a nickel oxide-yttria-stabilized zirconia composite cermet anode and a weight ratio of 6 to 10% yttria-stabilized zirconia (YSZ) or yttria-stabilized zirconia (SSZ) or yttria-doped yttria (CGO) electrolyte layer consisting of two layers, cast by casting, composite membrane area 100 ×100 (mm) 2 or more, the electrolyte thickness is 10 to 30 μm, and the anode thickness is 0.5 to 1.5 mm. Preferably, the anode is made of NiO+ (6-10%) mol The YSZ is composed of an electrolyte composed of one of 8YSZ, SSZ or CGO.
虽然这种复合膜平整并符合使用要求，但存在以下缺点：（1）8YSZ做电解质，离子导电率太低，产品功率密度低。阴极材料易与电解质中的ZrO 2 （氧化锆）反应影响电池的功率；（2）CGO材料电导率高，但由于易被阳极燃料气体还原，影响可靠性；（3）SSZ离子电导率高，但成本高，而且Sc（钪）在自然界及其稀缺，供应跟不上，无法形成量产；（4）NiO+(6～10)%mol YSZ材料强度低，做支撑体会影响可靠性。Although the composite film is flat and meets the requirements for use, it has the following disadvantages: (1) 8YSZ is used as an electrolyte, the ionic conductivity is too low, and the product power density is low. The cathode material easily reacts with ZrO 2 (zirconia) in the electrolyte to affect the power of the battery; (2) the CGO material has high conductivity, but is easily affected by the reduction of the anode fuel gas, affecting reliability; (3) the conductivity of the SSZ ion is high, However, the cost is high, and Sc (钪) is in the natural world and its scarcity, the supply cannot keep up, and mass production cannot be formed; (4) NiO+(6~10)%mol YSZ material has low strength, and the support will affect the reliability.
发明内容 Summary of the invention
针对现有技术的缺点，本发明提供了一种阳极支撑固体氧化物燃料电池，通过材料及结构设计有效提高单电池的功率密度，提高产品的机械强度及可靠性，降低生产成本，适用于批量化生产。 In view of the disadvantages of the prior art, the present invention provides an anode-supported solid oxide fuel cell, which effectively improves the power density of the single cell through material and structure design, improves the mechanical strength and reliability of the product, reduces the production cost, and is suitable for batch production. Production.
本发明还提供了一种阳极支撑固体氧化物燃料电池的制备方法，通过薄层流延工艺，既有效降低电解质的厚度，又保证了电解质的致密性。 The invention also provides a preparation method of an anode-supported solid oxide fuel cell, which can effectively reduce the thickness of the electrolyte and ensure the compactness of the electrolyte by the thin layer casting process.
为解决上述技术问题，本发明采用的技术方案是：In order to solve the above technical problems, the technical solution adopted by the present invention is:
一种阳极支撑固体氧化物燃料电池，其特征在于：依次由阳极支撑层、阳极功能层、燃料侧电解质层、空气侧电解质层以及阴极层组成； An anode-supported solid oxide fuel cell characterized by: sequentially comprising an anode support layer, an anode functional layer, a fuel side electrolyte layer, an air side electrolyte layer and a cathode layer;
所述阳极支撑层的组成为NiO+YSZ，其中，YSZ为2～6mol%氧化钇稳定的氧化锆，所述阳极功能层的组成为NiO+YSZ，其中，YSZ为5～12mol%氧化钇稳定的氧化锆，所述燃料侧电解质层的组成为5～12mol%氧化钇稳定的氧化锆，所述空气侧电解质层的组成为氧化铈或掺杂稀土的氧化铈。 The composition of the anode supporting layer is NiO+YSZ, wherein YSZ is 2-6 mol% yttria-stabilized zirconia, and the composition of the anode functional layer is NiO+YSZ, wherein YSZ is 5-12 mol% yttria stable The zirconia, the composition of the fuel-side electrolyte layer is 5 to 12 mol% of yttria-stabilized zirconia, and the composition of the air-side electrolyte layer is ruthenium oxide or rare earth-doped ruthenium oxide.
使用NiO（氧化镍）+ 2～6YSZ（2～6mol%钇稳定氧化锆）作为阳极支撑层材料，有效地提高了支撑体及单电池的强度； Use NiO (nickel oxide) + 2～6YSZ (2～6mol% yttrium stabilized zirconia) is used as the anode support layer material, which effectively improves the strength of the support and the single cell;
使用NiO（氧化镍）+ 5～12YSZ（5～12mol%钇稳定氧化锆）作为阳极功能层材料，有效地提高了三相界面的性能，降低了单电池极化电阻； Use NiO (nickel oxide) + 5～12YSZ (5～12mol% yttrium stabilized zirconia) is used as the anode functional layer material, which effectively improves the performance of the three-phase interface and reduces the polarization resistance of the single cell;
使用5～12YSZ（5～12mol%钇稳定氧化锆）和CeO 2 （氧化铈）或稀土掺杂CeO 2 作为双电解质材料，并使5～12YSZ（5～12mol%钇稳定氧化锆）靠近阳极侧（燃料侧），CeO 2 （氧化铈）或稀土掺杂CeO 2 靠近阴极侧（空气侧），有效地防止阴极与ZrO 2 （氧化锆）的反应，也有效地防止了燃料气与CeO 2 （氧化铈）或稀土掺杂CeO 2 的反应。5 to 12YSZ (5 to 12 mol% of yttria-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 are used as the dual electrolyte material, and 5 to 12 YSZ (5 to 12 mol% of yttrium-stabilized zirconia) is placed close to the anode side. (Fuel side), CeO 2 (yttria) or rare earth doped CeO 2 close to the cathode side (air side), effectively preventing the cathode from reacting with ZrO 2 (zirconia), and effectively preventing fuel gas and CeO 2 ( The reaction of cerium oxide or rare earth doped CeO 2 .
其中，所述阴极层为镧锶锰、镧锶钴铁、镧锶钴、镧钡钴铁、镧镍铁以及钡钴铁铌中的一种或几种。 Wherein, the cathode layer is one or more of cerium manganese, samarium cobalt iron, samarium cobalt, samarium cobalt iron, strontium nickel iron and samarium cobalt iron samarium.
可选地，所述阳极支撑层厚度为0.1～1.0mm，阳极功能层厚度为5～30μm，燃料侧电解质层厚度为0.5～15μm，空气侧电解质层厚度为0.5～15μm。 Optionally, the anode support layer has a thickness of 0.1 to 1.0 mm, the anode functional layer has a thickness of 5 to 30 μm, the fuel side electrolyte layer has a thickness of 0.5 to 15 μm, and the air side electrolyte layer has a thickness of 0.5 to 15 μm.
一种如上述阳极支撑固体氧化物燃料电池的制备方法，其特征在于，包括以下步骤： A method for preparing an anode-supported solid oxide fuel cell as described above, comprising the steps of:
（1）分别制备阳极支撑层陶瓷浆料、阳极功能层陶瓷浆料、燃料侧电解质层陶瓷浆料以及空气侧电解质层陶瓷浆料，流延制得阳极支撑层陶瓷膜带、阳极功能层陶瓷膜带、燃料侧电解质层陶瓷膜带以及空气侧电解质层陶瓷膜带； (1) Preparing an anode support layer ceramic slurry, an anode functional layer ceramic slurry, a fuel side electrolyte layer ceramic slurry, and an air side electrolyte layer ceramic slurry, respectively, and casting an anode support layer ceramic film tape and an anode functional layer ceramic Membrane tape, fuel side electrolyte layer ceramic film tape, and air side electrolyte layer ceramic film tape;
（2）将阳极支撑层陶瓷膜带、阳极功能层陶瓷膜带、燃料侧电解质层陶瓷膜带以及空气侧电解质层陶瓷膜带顺次叠层压合、烧结； (2) sequentially pressing and sintering the anode support layer ceramic film tape, the anode functional layer ceramic film tape, the fuel side electrolyte layer ceramic film tape, and the air side electrolyte layer ceramic film tape;
（3）将阴极材料制成印刷浆料，印刷在空气侧电解质层上，阴极进炉烧结。 (3) The cathode material is made into a printing paste, printed on the air-side electrolyte layer, and the cathode is sintered in the furnace.
与现有技术相比，本发明的有益效果是： Compared with the prior art, the beneficial effects of the present invention are:
本发明阳极支撑固体氧化物燃料电池，使用5～12YSZ（5～12mol%钇稳定氧化锆）和CeO 2 （氧化铈）或稀土掺杂CeO 2 作为双电解质材料，并使5～12YSZ（5～12mol%钇稳定氧化锆）靠近阳极侧（燃料侧），CeO 2 （氧化铈）或稀土掺杂CeO 2 靠近阴极侧（空气侧），有效地防止阴极与ZrO 2 （氧化锆）的反应，也有效地防止了燃料气与CeO 2 （氧化铈）或稀土掺杂CeO 2 的反应，大大提高了阳极支撑固体氧化物燃料电池的可靠性；The anode-supported solid oxide fuel cell of the present invention uses 5 to 12YSZ (5 to 12 mol% of yttrium-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 as a dual electrolyte material, and 5 to 12YSZ (5 to 5 12 mol% yttrium stabilized zirconia) close to the anode side (fuel side), CeO 2 (yttria) or rare earth doped CeO 2 close to the cathode side (air side), effectively preventing the cathode from reacting with ZrO 2 (zirconia), Effectively preventing the reaction of the fuel gas with CeO 2 (cerium oxide) or rare earth doped CeO 2 , greatly improving the reliability of the anode supported solid oxide fuel cell;
引入低成本材料，使用NiO（氧化镍）+ 2～6YSZ（2～6mol%钇稳定氧化锆）作为阳极支撑层材料、NiO（氧化镍）+ 5～12YSZ（5～12mol%钇稳定氧化锆）作为阳极功能层材料、5～12YSZ（5～12mol%钇稳定氧化锆）和CeO 2 （氧化铈）或稀土掺杂CeO 2 作为双电解质材料，可适于批量化生产。Introducing low-cost materials using NiO (nickel oxide) + 2 ~ 6YSZ (2 ~ 6mol% yttria stabilized zirconia) as anode support layer material, NiO (nickel oxide) + 5 ~ 12YSZ (5 ~ 12mol% yttria stabilized zirconia) As the anode functional layer material, 5 to 12YSZ (5 to 12 mol% of yttrium-stabilized zirconia) and CeO 2 (yttria) or rare earth doped CeO 2 can be suitably used for mass production.
本发明阳极支撑固体氧化物燃料电池的制备方法，采用可批量化生产的低成本流延工艺制作阳极支撑层、阳极功能层以及电解质层，采用印刷工艺制作阴极层，通过薄层流延工艺有效降低了电解质层的厚度（0.5～15μm），并使用高离子导电的CeO 2 （氧化铈）或稀土掺杂CeO 2 作为电解质材料，提高了电解质离子的导电能力；使用NiO（氧化镍）+ 5～12YSZ（5～12mol%钇稳定氧化锆）作为阳极功能层材料，阳极支撑层、阳极功能层以及双电解质层生片叠层压合一体后共烧结，有效提高了阳极与电解质界面的性能。The preparation method of the anode-supported solid oxide fuel cell of the invention adopts a low-cost casting process capable of mass production to fabricate an anode support layer, an anode functional layer and an electrolyte layer, and a cathode layer is formed by a printing process, which is effective by a thin layer casting process. Reduce the thickness of the electrolyte layer (0.5 to 15 μm) and use high-ion-conducting CeO 2 (yttria) or rare earth doped CeO 2 as the electrolyte material to improve the conductivity of the electrolyte ions; use NiO (nickel oxide) + 5 ～12YSZ (5～12mol% yttrium-stabilized zirconia) is used as the anode functional layer material, and the anode support layer, the anode functional layer and the double electrolyte layer green sheets are laminated and integrated together, thereby effectively improving the performance of the anode-electrolyte interface.
附图说明 DRAWINGS
图1为本发明阳极支撑固体氧化物燃料电池的剖面图。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing an anode supported solid oxide fuel cell of the present invention.
具体实施方式 detailed description
下面结合具体实施方式对本发明作进一步的说明。 The invention will now be further described in conjunction with specific embodiments.
如图1所示为本发明阳极支撑固体氧化物燃料电池的实施例，该阳极支撑固体氧化物燃料电池依次由阳极支撑层1、阳极功能层2、燃料侧电解质层3、空气侧电解质层4以及阴极层5组成。 1 is an embodiment of an anode supported solid oxide fuel cell of the present invention. The anode supported solid oxide fuel cell is sequentially composed of an anode supporting layer 1, an anode functional layer 2, a fuel side electrolyte layer 3, and an air side electrolyte layer 4. And the cathode layer 5 is composed.
首先分别制备阳极支撑层1陶瓷浆料，其成分为1：1的5YSZ（5mol%钇稳定氧化锆）+NiO（氧化镍）；阳极功能层2陶瓷浆料，其成分为1：1的10YSZ（10mol%钇稳定氧化锆）+NiO（氧化镍）；燃料侧电解质层3陶瓷浆料，其成分为10YSZ（10mol%钇稳定氧化锆）；空气侧电解质层4陶瓷浆料，其成分为GOC（镓掺杂氧化铈）； Firstly, the anode support layer 1 ceramic slurry was prepared separately, and its composition was 1:1 5YSZ (5mol% yttrium stabilized zirconia) + NiO (nickel oxide); anode functional layer 2 ceramic slurry, its composition was 1:1 10YSZ (10 mol% yttrium stabilized zirconia) + NiO (nickel oxide); fuel side electrolyte layer 3 ceramic slurry, the composition of which is 10YSZ (10 mol% yttrium stabilized zirconia); air side electrolyte layer 4 ceramic slurry, the composition of which is GOC (gallium doped yttrium oxide);
接着通过流延方法制得阳极支撑层1陶瓷膜带、阳极功能层2陶瓷膜带、燃料侧电解质层3陶瓷膜带以及空气侧电解质层4陶瓷膜带； Then, an anode support layer 1 ceramic film tape, an anode functional layer 2 ceramic film tape, a fuel side electrolyte layer 3 ceramic film tape, and an air side electrolyte layer 4 ceramic film tape are prepared by a casting method;
然后将阳极支撑层1陶瓷膜带、阳极功能层2陶瓷膜带、燃料侧电解质层3陶瓷膜带以及空气侧电解质层4陶瓷膜带顺次进行叠层压合、烧结，之后在空气侧电解质层上印刷LSCF（镧锶钴铁）阴极层5，最后进行阴极烧结。 Then, the anode support layer 1 ceramic film tape, the anode functional layer 2 ceramic film tape, the fuel side electrolyte layer 3 ceramic film tape, and the air side electrolyte layer 4 ceramic film tape are sequentially laminated and pressed, and then sintered on the air side electrolyte. The LSCF (samarium cobalt iron) cathode layer 5 is printed on the layer, and finally cathode sintering is performed.
由上述制备方法制得阳极支撑固体氧化物燃料电池，其阳极支撑层1厚度为0.5 mm，阳极功能层2厚度为15μm，燃料侧电解质层3厚度为10μm，空气侧电解质层4厚度为10μm。测得电池在800℃时的功率密度：0.45W/cm2，1000hr衰减：0.31%。 An anode-supported solid oxide fuel cell is obtained by the above preparation method, and the anode support layer 1 has a thickness of 0.5 In mm, the anode functional layer 2 has a thickness of 15 μm, the fuel-side electrolyte layer 3 has a thickness of 10 μm, and the air-side electrolyte layer 4 has a thickness of 10 μm. The power density of the battery at 800 ° C was measured: 0.45 W/cm 2 , 1000 hr attenuation: 0.31%.
采用本实施例阳极支撑固体氧化物燃料电池制备方法制得的阳极支撑固体氧化物燃料电池，通过材料及结构的设计有效提高了单电池的功率密度及产品的机械强度，导电能力好，可靠性高，成本低，适于批量化生产；通过薄层流延工艺，既有效降低电解质的厚度，又保证了电解质的致密性。 The anode-supported solid oxide fuel cell prepared by the method for preparing the anode-supported solid oxide fuel cell of the present embodiment effectively improves the power density of the single cell and the mechanical strength of the product through the design of materials and structures, and has good electrical conductivity and reliability. High, low cost, suitable for mass production; through the thin layer casting process, it not only effectively reduces the thickness of the electrolyte, but also ensures the compactness of the electrolyte.

Claims (5)

  1. 一种阳极支撑固体氧化物燃料电池，其特征在于：依次由阳极支撑层、阳极功能层、燃料侧电解质层、空气侧电解质层以及阴极层组成。An anode-supported solid oxide fuel cell characterized by comprising an anode support layer, an anode functional layer, a fuel side electrolyte layer, an air side electrolyte layer, and a cathode layer in this order.
  2. 根据权利要求1所述的阳极支撑固体氧化物燃料电池，其特征在于：The anode supported solid oxide fuel cell of claim 1 wherein:
    所述阳极支撑层的组成为NiO+YSZ，其中，YSZ为2～6mol%氧化钇稳定的氧化锆，The composition of the anode support layer is NiO+YSZ, wherein YSZ is 2-6 mol% yttria-stabilized zirconia,
    所述阳极功能层的组成为NiO+YSZ，其中，YSZ为5～12mol%氧化钇稳定的氧化锆，The composition of the anode functional layer is NiO+YSZ, wherein YSZ is 5-12 mol% yttria-stabilized zirconia,
    所述燃料侧电解质层的组成为5～12mol%氧化钇稳定的氧化锆，The composition of the fuel-side electrolyte layer is 5 to 12 mol% of yttria-stabilized zirconia,
    所述空气侧电解质层的组成为氧化铈或掺杂稀土的氧化铈。The composition of the air-side electrolyte layer is cerium oxide or rare earth-doped cerium oxide.
  3. 根据权利要求2所述的阳极支撑固体氧化物燃料电池，其特征在于：所述阴极层为镧锶锰、镧锶钴铁、镧锶钴、镧钡钴铁、镧镍铁以及钡钴铁铌中的一种或几种。The anode-supported solid oxide fuel cell according to claim 2, wherein the cathode layer is lanthanum manganese, samarium cobalt iron, samarium cobalt, samarium cobalt iron, lanthanum nickel iron, and samarium cobalt samarium One or several of them.
  4. 根据权利要求1所述的阳极支撑固体氧化物燃料电池，其特征在于：所述阳极支撑层厚度为0.1～1.0mm，阳极功能层厚度为5～30μm，燃料侧电解质层厚度为0.5～15μm，空气侧电解质层厚度为0.5～15μm。The anode-supported solid oxide fuel cell according to claim 1, wherein the anode supporting layer has a thickness of 0.1 to 1.0 mm, the anode functional layer has a thickness of 5 to 30 μm, and the fuel side electrolyte layer has a thickness of 0.5 to 15 μm. The thickness of the air side electrolyte layer is 0.5 to 15 μm.
  5. 一种如权利要求1至4任一项所述的阳极支撑固体氧化物燃料电池的制备方法，其特征在于，包括以下步骤：A method of preparing an anode-supported solid oxide fuel cell according to any one of claims 1 to 4, comprising the steps of:
    分别制备阳极支撑层陶瓷浆料、阳极功能层陶瓷浆料、燃料侧电解质层陶瓷浆料以及空气侧电解质层陶瓷浆料，流延制得阳极支撑层陶瓷膜带、阳极功能层陶瓷膜带、燃料侧电解质层陶瓷膜带以及空气侧电解质层陶瓷膜带；The anode support layer ceramic slurry, the anode functional layer ceramic slurry, the fuel side electrolyte layer ceramic slurry, and the air side electrolyte layer ceramic slurry are respectively prepared, and the anode support layer ceramic film tape and the anode functional layer ceramic film tape are cast and cast. a fuel side electrolyte layer ceramic film tape and an air side electrolyte layer ceramic film tape;
    将阳极支撑层陶瓷膜带、阳极功能层陶瓷膜带、燃料侧电解质层陶瓷膜带以及空气侧电解质层陶瓷膜带顺次叠层压合、烧结；The anode support layer ceramic film tape, the anode functional layer ceramic film tape, the fuel side electrolyte layer ceramic film tape, and the air side electrolyte layer ceramic film tape are sequentially laminated and sintered;
    将阴极材料制成印刷浆料，印刷在空气侧电解质层上，阴极进炉烧结。The cathode material is made into a printing paste, printed on the air side electrolyte layer, and the cathode is sintered in the furnace.
PCT/CN2012/075915 2012-05-22 2012-05-22 Anode-supported solid oxide fuel cell and method for preparing same WO2013173981A1 (en)

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