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WO2008047322A2 - Membrane electrode group for solid oxide fuel cell - Google Patents

Membrane electrode group for solid oxide fuel cell Download PDF

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Publication number
WO2008047322A2
WO2008047322A2 PCT/IB2007/054241 IB2007054241W WO2008047322A2 WO 2008047322 A2 WO2008047322 A2 WO 2008047322A2 IB 2007054241 W IB2007054241 W IB 2007054241W WO 2008047322 A2 WO2008047322 A2 WO 2008047322A2
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WIPO (PCT)
Prior art keywords
current collector
electrolyte
fuel cells
membrane
solid oxide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2007/054241
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French (fr)
Other versions
WO2008047322A3 (en
Inventor
Sadig Guliyev
Beycan Ibrahimoglu
Rafig Alibeyli
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Vestel Elektronik Sanayi ve Ticaret AS
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Vestel Elektronik Sanayi ve Ticaret AS
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Publication of WO2008047322A3 publication Critical patent/WO2008047322A3/en
Anticipated expiration legal-status Critical
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8878Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882Heat treatment, e.g. drying, baking
    • H01M4/8885Sintering or firing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9041Metals or alloys
    • H01M4/905Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/12Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124Fuel 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
    • H01M8/1246Fuel 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
    • H01M8/126Fuel 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Fuel cells are devices converting chemical energy into electrical energy. Fuel cells are made of from several to hundreds of cells depending on their power rates and sizes. A simple fuel cell is composed of a cell, whereas the cell is built up from two current collectors and a membrane electrode group interposed between these current collectors.
  • the fuel cells have the following advantages as compared to conventional power production systems: very low environmental pollution rates, very high energy production efficiency, - workable with different fuels, recoverability of consumed heat, high development potential, workable at low temperature and pressure, and workable together with or separately from the network.
  • very low environmental pollution rates very high energy production efficiency
  • - workable with different fuels recoverability of consumed heat
  • high development potential workable at low temperature and pressure
  • workable together with or separately from the network are available:
  • DMFC Direct Methanol Fuel Cells
  • RFC Regenerative Fuel Cells
  • Fuel cells are classified according to the fuel type they employ and the temperature they work in.
  • One of the most significant components of fuel cells is the membrane.
  • the fuel cells are also differentiated according to the membrane (electrolyte) types they make use of.
  • the membranes define a fuel cell's volt-ampere characterization.
  • Various membranes are being produced nowadays with different purposes. For instance, "direct methanol” and “proton permeable” fuel cells employ solid polymer electrolytes (membranes). The operation temperature of such membranes varies between 80 to 100 0 C, whereas Nafion type membranes in various thicknesses are mostly used in fuel cells.
  • CH 4 C+2H 2 - Direct reaction of methane.
  • the hydrogen gas (H 2 ) decomposed at high temperature fills the hydrogen chamber, shown with reference number "4" in Figure 1. Hydrogen gas (H 2 ) in the hydrogen chamber then contacts the electrode (anode) (5). Oxygen (O 2 ) or air at the same temperature contacts the electrode (cathode) (7) within the oxygen chamber (6) to give an electrochemical reaction with the support of the solid oxide electrolyte (8).
  • the membrane Since the membrane is deposited on the current collector, it is easily assembled.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The present invention relates to directly depositing the anode, cathode, and electrolyte materials on the current collector by means of physical and chemical methods, in place of using a single-piece membrane group in solid oxide fuel cells (SOFC). Such electrolyte material is ceramic and is deposited on the electrodes (5), (7) and on the electrolyte (8) current collector (9) by means of physical and chemical methods. In this method, the Current collector-Catalyst-Membrane are brought together and designed in this fashion. The membranes designed in this fashion constitute one cell in fuel cells. As for the fuel cell, it is composed by interconnecting the cells depending on the aimed power rate.

Description

DESCRIPTION
MEMBRANE ELECTRODE GROUP FOR SOLID OXIDE FUEL CELL TECHNICAL FIELD
The present invention relates to directly depositing the anode, cathode, and electrolyte materials on the current collector by means of physical and chemical methods, in place of a single-piece membrane group used in Solid Oxide Fuel Cells (SOFC). Such electrolyte material is ceramic and is deposited on the electrodes (5, 7) and on the electrolyte (8) current collector (9) by means of physical and chemical methods. In this method, the
Current collector-Catalyst-Membrane are brought together and designed in this fashion. The membranes designed in this fashion constitute one cell in fuel cells. As for the fuel cell, it is composed by interconnecting the cells depending on the aimed power rate.
TECHNICAL PROBLEMS THE PRESENT INVENTION AIMS TO SOLVE
Fuel cells are devices converting chemical energy into electrical energy. Fuel cells are made of from several to hundreds of cells depending on their power rates and sizes. A simple fuel cell is composed of a cell, whereas the cell is built up from two current collectors and a membrane electrode group interposed between these current collectors.
The most pronounced feature of novel technologies nowadays is that they operate at proper conditions by ensuring ecological, clean, safe, and high-efficiencies. The fuel cells, called as the technology wonder of the 21st century, do satisfactorily fulfill the aforesaid criteria.
Furthermore, the fuel cells have the following advantages as compared to conventional power production systems: very low environmental pollution rates, very high energy production efficiency, - workable with different fuels, recoverability of consumed heat, high development potential, workable at low temperature and pressure, and workable together with or separately from the network. Presently, the following fuel cells are available:
Proton Exchange Membranes (PEM), Cylindrical Proton Exchange Membranes (CPEM), Alkaline Fuel Cells (AFC), Phosphoric Acid Fuel Cells (PAFC), Molten Carbonate Fuel Cells (MCFC) - Solid Oxide Fuel Cells (SOFC),
Direct Methanol Fuel Cells (DMFC), and Regenerative Fuel Cells (RFC), etc.
Fuel cells are classified according to the fuel type they employ and the temperature they work in. One of the most significant components of fuel cells is the membrane. The fuel cells are also differentiated according to the membrane (electrolyte) types they make use of. The membranes define a fuel cell's volt-ampere characterization. Various membranes are being produced nowadays with different purposes. For instance, "direct methanol" and "proton permeable" fuel cells employ solid polymer electrolytes (membranes). The operation temperature of such membranes varies between 80 to 1000C, whereas Nafion type membranes in various thicknesses are mostly used in fuel cells.
One of the fuel cell types having attracted great attention with respect to researches in recent years is the Solid Oxide Fuel Cells, which operate at higher temperatures (to be referred to hereinafter as SOFC). The operating temperature of such type of fuel cells vary between 800 and 10000C and they make use of natural gas, methane, LPG, etc. as the fuel source. They have reached up to 80% in efficiency.
Ceramic electrodes are used in SOFC.
SOFC — membrane electrode group— is a ceramic material with a thickness of 25 to 100 microns, which is brought into a single piece by interposing it between two electrodes then sintering it at high temperatures. Three interdependent processes occur during the manufacture of SOFC.
1. The separation process of hydrogen gas (H2) catalytically from fuels (natural gas, methane, LPC, and similar gases).
2. Direct current production process resulting from reduction and oxidation reactions of hydrogen and oxygen gases within the fuel cell. 3. Heat-aimed use process of the temperature generated as a result of such reactions.
The First Process: The production of hydrogen gas (H2) as a result of catalytic conversion from the methane gas (CH4) is conducted by means of three methods supported by a catalyst at high temperatures of 650-8000C.
In the first method, the reactor is fed with water along with the methane gas.
In the second method, oxygen gas or air is supplied together with the methane gas into the reactor so as to conduct the reaction in an anhydrous medium. As for the third method, only methane gas is introduced into the reactor. The advantages and disadvantages of all three methods are known.
The researches report that the conversion of methane gas (CH4) to hydrogen gas (H2) may reach up to 93% at high temperatures (7500C).
CH4 + H2O = CO +3H2 - Reaction of methane with water vapor, CH4 + 1/2O2 = CO +2H2 - Partial oxidation reaction of methane with oxygen,
CH4 = C + 2H2 - Direct decomposition reaction of methane.
The Second Process: The hydrogen gas (H2) decomposed from the methane gas (CH4) catalytically and the oxygen gas (O2) or air brought to the same temperature are introduced into the fuel cell. Hydrogen and oxygen gases included in the fuel cell combine with the membrane electrode group to give the electrochemical reaction. Direct current is obtained as a result of the electrochemical reaction. This reaction takes place exothermically. As the heat increases, the efficiency of the fuel cell is enhanced as well.
Current producing reaction:
At the anode: H2 + O2" — H2O + 2e~ At the cathode: O2 + 4e 2O2"
The Third Process: A certain amount of heat is released in addition to the electrical energy produced during the operation of the fuel cells. This temperature reaches to 500-8000C in SOFCs.
It has been focused on making use of this generated heat for various purposes in designing the fuel cells lately.
In Schema 5 is schematically illustrated all three process occurring in the SOFC system. WORKING PRINCIPLE OF SOFC SYSTEM Figure 1 : 1- Reactor 2- Catalyst 3- Heater 4- Hydrogen chamber
5- Anode electrode
6- Oxygen chamber
7- Cathode electrode 10- Resistance
Figure 2:
4- Hydrogen chamber
5- Anode electrode
6- Oxygen chamber 7- Cathode electrode
8- Electrolyte Figure 3:
5- Anode electrode
7- Cathode electrode 8- Electrolyte
Figure 4:
4- Hydrogen chamber
5- Anode electrode 7- Cathode electrode 8- Electrolyte
9- Current collector
After the reactor (1) with a catalyst (2) introduced into it is externally heated (650-8000C) by means of any heater (3) (accumulator, burner, etc.), the fuel (natural gas, methane LPG, etc.) is supplied into the reactor. The fuel in the reactor then combines with the catalyst (2) that has already reached a certain temperature, and gives the following decomposition reactions:
CH4 + H2O = CO +3H2 - Reaction of methane with water,
CH4 + 1/2O2= CO +2H2 - Partial oxidation reaction of methane with oxygen,
CH4 = C+2H2 - Direct reaction of methane. The hydrogen gas (H2) decomposed at high temperature fills the hydrogen chamber, shown with reference number "4" in Figure 1. Hydrogen gas (H2) in the hydrogen chamber then contacts the electrode (anode) (5). Oxygen (O2) or air at the same temperature contacts the electrode (cathode) (7) within the oxygen chamber (6) to give an electrochemical reaction with the support of the solid oxide electrolyte (8).
As illustrated in Figure 2, nowadays the electrodes (5), (7) and the electrolyte (8) are being brought into a single-piece membrane electrode system with a thickness of about 25 to 100μ under high temperature conditions (12000C). [ 1 , 2, 3... ]
The typically used material as the membrane material in a SOFC system is zirconium stabilized with yttrium (YSZ, Zr1-xYxO2-δ). This material shows a very high ionic conductivity at 10000C (0.02 S/m at 8000C, 0.1 S/m at 1000°C). The feature that this material represents a stable structure with low electron conductivity at higher temperatures makes this material attractive. Since the ionic conductivity substantially decreases at temperatures below 10000C, it becomes impossible to descend to lower working temperatures. There have been intense researches, however, for lower working temperatures. Such researches are focused on cerium alloys, titanium alloys, lanthanum alloys, etc. Such researches have revealed that at 9000C the CeO.8GdO.202 combination reaches ionic conduction of the 0.1 s/cm that YSZ shows at 10000C. The material La0.8Sr0.2Ga0.8Mg0.13Ni0.07O3 lowers down the working temperature to 700°C. With respect to the present invention, no single-piece membrane is included in the fuel cell. The membrane material —as shown in Figure 3— is deposited on the electrodes (5), (7) and on the electrolytic (8) current collector (9) by means of pressing and of physicochemical methods. In this method, the Current collector-Catalyst-Membrane are brought together and designed in this fashion. This system makes also one cell. As illustrated in Figure 4, the current collector (9) is made from a metallic material with high conductivity, which has an expansion coefficient equal to expansion coefficients of ceramic membrane materials, and which does not undergo corrosion even at high temperatures. The hydrogen chamber (4) is formed within the current collector (9). The hydrogen gas within the hydrogen chamber (4) comes out through the holes (10) on the current collector (9) to contact the anode electrode (5), whereas the oxygen gas makes this contact externally with the cathode electrode (7).
The Current Collector-Catalyst-Membrane group according to the present invention has the following advantages as compared to the conventionally made membranes:
Since the membrane is deposited on the current collector, any break of it is not observed. It has a more cost-efficient production.
Lower temperatures are required for producing the membrane.
Since the membrane is deposited on the current collector, it is easily assembled.
The deposition of the membrane on the current collector and baking them together forms a single cell.
PRODUCTION OF THE CURRENT COLLECTOR-MEMBRANE GROUP
Whilst numerous different membranes are made at various laboratories lately, such membranes with ideal characteristics haven't been made yet. The characteristics that the membranes are expected to possess are as follows: 1. High ion permeability,
2. resistance to oxidation and reduction,
3. resistance to prolonged temperature and current intensity,
4. mechanical rigidity,
5. workability with different catalysts, 6. inexpensiveness, etc.
The following materials are used in the subject Current Collector-Catalyst-Membrane group:
Anode
NiO/GDC Gadolinium Doped Ceria. (Ce0.9Gd0.1) 01.95
Cathode
60% LSF20 , 40% GDC Mixture
LSF20 (LaO.80 Sr0.20)0.995 Fe 03-x
GDC Ce0.9Gd0.1)O1.95 Electrolyte
Gadolinium Doped Ceria. (Ce0.9Gd0.1)O1.95
The current collector-catalyst-membrane group is produced according to the following sequence. At first, a current collector (9) is made with small-diameter orifices opened on both sides thereof from a metallic material, which has a high conductivity and does not undergo corrosion at high temperatures (see Figure 4). The expansion coefficient of the current collector is equal to the expansion coefficient of ceramic membrane materials.
The materia) NiO/GDC Gadolinium Doped Ceria. (Ce0.9Gd0.1) 01.9 with a thickness of 10-15 micron is deposited in the form of slurry as the first layer on the anode (5) surface of the current collector. After the first layer is heated to 1000C, it is slowly cooled down and dried. As the second layer, polymer and polymer-solving materials together with dispersant materials are brought into high viscosity slurry in the electrolyte (8) made from the Gadolinium Doped Ceria. (Ce0.9Gd0.1) 01.95 material. The Gadolinium Doped Ceria material, now in the form of slurry, is deposited on the first layer by a thickness of 5-15 micron, and after the second layer is coated, it is put back into an oven at 100°C-150°C, and then dried for deposing the third layer. The third layer electrolyte cathode (7) materials are prepared from the followings: 60% LSF20, 40% GDC Mixture LSF20 (LaO.80 Sr0.20)0.995 Fe 03-X GDC Ce0.9Gd0.1) 01.95. The third layer is also deposited on the second current collector or it is coated on the current collector, the upper surface of which is coated with the electrode (5) and electrolyte (8). After all deposition processes are completed, the current collector, the upper surface of which is coated with electrode and electrolyte materials is heated to 10000C within an oven, and then it is cooled slowly so as to obtain the current collector-membrane group. The resulting current collector-membrane group now can be used in place of the single- piece membrane within the fuel cell.

Claims

1. A direct depositing the anode (5), cathode (7), and electrolyte materials (8) on the current collector (9) by means of physical and chemical methods, in place of using a single-piece membrane group in solid oxide fuel cells (SOFC).
2. An anode electrode (5) according to Claim 1 , characterized in that it is coated with a catalyst material (preferably NiO/GDC Gadolinium Doped Ceria. (Ce0.9Gd0.1)O1.9) of 10-15 micron thickness and then heated to 1000C.
3. An electrolyte (8) material according to Claim 1 , characterized in that it is deposited on the anode electrode by making use of a ceramic material (preferably Gadolinium Doped Ceria. (Ce0.9Gd0.1) 01.95), and dried again up to 1000C.
4. A cathode (7) electrode according to Claim 1 , characterized in that it is coated with a catalyst material (preferably 60% LSF20, 40% GDC Mixture LSF20(La0.80 SrO.20)0.995 Fe 03-X GDC eθ.9GdO.1)01.95) of 10-15 micron thickness on the electrolyte and heated to 100°C.
5. A membrane group according to Claim 1 , characterized in that it is sintered at 1000°C after the process in claims 2- 4 are completed.
PCT/IB2007/054241 2006-10-19 2007-10-18 Membrane electrode group for solid oxide fuel cell Ceased WO2008047322A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2006/05864 2006-10-19
TR2006/05864A TR200605864A2 (en) 2006-10-19 2006-10-19 Membrane electrode assembly for solid oxide fuel cell.

Publications (2)

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WO2008047322A2 true WO2008047322A2 (en) 2008-04-24
WO2008047322A3 WO2008047322A3 (en) 2008-06-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119627163A (en) * 2024-12-06 2025-03-14 浙江大学 Preparation method and use of electrolyte for solid oxide fuel cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230849A (en) * 1991-06-04 1993-07-27 Michael S. Hsu Electrochemical converter assembly and overlay methods of forming component structures
US5753385A (en) * 1995-12-12 1998-05-19 Regents Of The University Of California Hybrid deposition of thin film solid oxide fuel cells and electrolyzers
JP3841149B2 (en) * 2001-05-01 2006-11-01 日産自動車株式会社 Single cell for solid oxide fuel cell
US6495279B1 (en) * 2001-10-02 2002-12-17 Ford Global Technologies, Inc. Ultrahigh power density miniaturized solid-oxide fuel cell
US6893762B2 (en) * 2002-01-16 2005-05-17 Alberta Research Council, Inc. Metal-supported tubular micro-fuel cell
US7244526B1 (en) * 2003-04-28 2007-07-17 Battelle Memorial Institute Solid oxide fuel cell anodes and electrodes for other electrochemical devices

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119627163A (en) * 2024-12-06 2025-03-14 浙江大学 Preparation method and use of electrolyte for solid oxide fuel cell

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TR200605864A2 (en) 2007-03-21

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