WO2010045329A2 - Advanced materials and design for low temperature sofcs - Google Patents
Advanced materials and design for low temperature sofcs Download PDFInfo
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- WO2010045329A2 WO2010045329A2 PCT/US2009/060643 US2009060643W WO2010045329A2 WO 2010045329 A2 WO2010045329 A2 WO 2010045329A2 US 2009060643 W US2009060643 W US 2009060643W WO 2010045329 A2 WO2010045329 A2 WO 2010045329A2
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1266—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 bismuth oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- a fuel cell is an electrochemical device that converts chemical energy in the oxidation of fuels (such as hydrogen, methane, butane or even gasoline and diesel) into electrical energy.
- Fuel cells are simple devices that contain no moving parts, consisting essentially of four functional elements: cathodes, electrolytes, anodes and interconnects.
- Solid oxide fuel cells (SOFCs) are attractive because of their ability to convert a wide variety of fuels to electrical energy with a high efficiency of up to 70% in pressurized systems as compared to engines and modern thermal power plants that typically show a maximum of 40% efficiency. In applications designed to capture the SOFCs waste heat for co-generation, the overall efficiency can top 80 percent.
- SOFC technology has the distinct advantage over competing fuel cell technologies (e.g. molten carbonate, polymer electrolyte, phosphoric acid and alkali) because of its ability to use fuels other than hydrogen and their relative insensitivity to CO, which act as poisons to other fuel cell types.
- the general design is that of two porous electrodes separated by a ceramic electrolyte.
- the oxygen source typically air, contacts the cathode to form oxygen ions upon reduction by electrons at the cathode/electrolyte interface.
- the oxygen ions diffuse through the electrolyte material to the anode where the oxygen ions encounter the fuel at the anode/electrolyte interface forming, water, carbon dioxide (with hydrocarbon fuels), heat, and electrons.
- the electrons transport from the anode through an external circuit to the cathode.
- SOFCs are, in concept, simple, the identification of efficient materials for the components remains an enormous challenge. These materials must have the electrical properties required, yet be chemically and structurally stable.
- SOFCs operate at temperatures of about 1000 0 C to achieve sufficiently high current densities and power.
- the reactivity of the components with each other and/or the oxygen and/or the fuel and the interdiffusion between components presents a challenge at the high temperatures.
- the thermal expansion coefficients of the materials must be sufficiently matched to minimize thermal stresses that can lead to cracking and mechanical failure.
- the air side of the cell must operate in an oxidizing atmosphere and the fuel side must operate in a reducing atmosphere.
- Yttria-stabilized zirconia serves the dual purpose of stabilizing zirconia in the cubic structure at low temperatures and providing oxygen vacancies.
- doped cerium oxide and doped bismuth oxide have shown some promise, however, neither are sufficient to perform as needed.
- Bismuth oxide-based electrolytes have high oxygen ion conductivities sufficient for low temperature operations (less than 800 0 C) but require high P 02 levels for sufficient thermodynamic stability. Low P 0 2 at the anode promotes bismuth oxide decomposition, and results in failure of the SOFC.
- Cerium oxide based electrolytes have the advantage of high ionic conductivity in air and can operate effectively at low temperatures (under 700 0 C). However, these electrolytes are susceptible to reduction of Ce +4 to Ce ⁇ 3 on the anode, leading to electronic conductivity and a leakage current between the anode and cathode. A temperature below 700 0 C significantly broadens the choice of materials for the cathodes, anodes, and interconnects, which allows for the use of much less expensive and more readily available materials than those used currently for SOFCs.
- the anode and cathode need improvements to form excellent SOFCs. Improvements not only involve identifying superior materials, but also identifying improvement of the triple phase boundary between the electrode, electrolyte, and oxygen or fuel. Hence, viable low temperature SOFC requires identification of a system, materials, structure and fabrication techniques that maximizes efficiency at the minimum temperature.
- Embodiments of the invention are directed to solid oxide fuel cells (SOFCs) comprising a multilayer structure that comprise a porous metal-ceramic anode with an anodic functional layer (AFL) coupling the anode to a bilayer electrolyte having a cerium oxide comprising layer and a bismuth oxide comprising layer and a porous ceramic cathode.
- SOFCs function at temperatures below 700 0 C and display a power density of at least 1 Wcm 2 at 650 0 C.
- the SOFC includes metal or metal alloy interconnects to the electrodes, for example, stainless steel interconnects.
- the cerium oxide comprising layer of the bilayer electrolyte can be Ce x Sm 1-X O 2-S
- the bismuth oxide comprising layer can be Bi 2-x Er x 0 3 (ESB), Bi 2-x Dw x 0 3 (DSB), Bi 2-x Y ⁇ 0 3 (YSB), or Bi 2-(x+y) Dy x W y O 3 (DWSB).
- ESD Er x 0 3
- DSB Bi 2-x Dw x 0 3
- YSB Bi 2-x Y ⁇ 0 3
- DWSB Bi 2-(x+y) Dy x W y O 3
- the values of x or x+y can range from less than 0.1 to about 0.5 and y can range from 0.01 to 0.49.
- the bilayer electrolyte can be less than or equal to 100 ⁇ m in thickness.
- the bismuth oxide comprising layer of the bilayer electrolyte can be less than or equal to 20 ⁇ m in thickness. In some embodiments of the invention, the bismuth oxide comprising layer can be at least 1% of the thickness of the cerium oxide comprising layer. In some embodiments of the invention, the bismuth oxide comprising layer can be at least 10% of the thickness of the cerium oxide comprising layer.
- the metal-ceramic anode in its oxidized form can be a blend of NiO or CuO with a cerium comprising electrolyte.
- the cerium comprising electrolyte can be Ce x Sm] -x O 2- s (SDC), Ce x Gd 1-x 0 2- g (GDC) or Sm x NdyCei -x-y ⁇ 2 - 5 .
- the AFL coupling the anode to the bilayer electrolyte can be a cerium oxide comprising compound of like composition to the cerium oxide comprising compound in the metal-ceramic anode and/or of the bilayer electrolyte where the AFL 's cerium oxide comprising compound is of a smaller particle size than the particles of the cerium oxide comprising compound in the anode.
- the AFL' s cerium oxide comprising compound can include the metal oxide of the metal-ceramic anode.
- the porous ceramic cathode can be Bi 2 Ru 2 O 7 (BRO7), BR07-(Er 2 0 3 )o. 2 (Bi 2 0 3 )o .8 (ESB) composite, BRO-(Dw 2 0 3 )o. 2 (Bi 2 0 3 )o. 8 ) (DSB) composite, BRO-(Y 2 0 3 )o, 2 (Bi 2 0 3 )o. 8 ) (YSB) composite or BRO-Bi 2- ( X+ y ) Dy x W y O 3 (DWSB) composite.
- the cathode can be coupled to the bilayer electrolyte by a cathodic functional layer (CFL).
- the CFL can be a bismuth oxide comprising compound of the same chemical composition as the bismuth oxide comprising layer of the bilayer electrolyte and of a composite cathode.
- Other embodiments of the invention are directed to a method for preparing the SOFC where an AFL is formed on the metal-ceramic anode, upon which the cerium oxide comprising layer of the bilayer electrolyte is deposited on the AFL followed by depositing the bismuth oxide comprising layer on the cerium oxide comprising layer to complete the a bilayer electrolyte, and depositing a porous ceramic cathode on the bismuth oxide comprising layer.
- the AFL can be formed by depositing a GDC or Ni-GDC precursor solution on the metal-ceramic anode surface and heat-treating the resulting precursor coated metal-ceramic anode.
- the bismuth oxide comprising layer can be deposited using pulsed laser deposition (PLD).
- cerium oxide comprising layer can be deposited using pulsed laser deposition (PLD).
- Figure 1 is a representation of the nature of a GDC AFL coating on a NiO-GDC anode according to an embodiment of the invention.
- Figure 2 is a SEM micrograph of the cross-section of a SOFC with a BRO7/BRO7-
- ESB cathode/(ESB/GDC) bilayer electrolyte/Ni-GDC anode with a thick (1-2 mm) anode and a thick bilayer electrolyte (55 ⁇ m GDC/ 20 ⁇ m ESB) prepared by co-pressing the GDC onto the Ni-GDC anode support and screen-printing the ESB on the GDC after it was sintered.
- Figure 3 illustrates the bilayer electrolyte layer approach to a stable electrolyte layer according to embodiments of the invention where the relative thickness of the bilayers avoids an interfacial oxygen partial pressure (Po 2 ) level where decomposition occurs.
- Po 2 interfacial oxygen partial pressure
- Figure 4 shows (a) a SEM micrograph of the cross-section of the ESB/GDC bilayer electrolyte on Ni-GDC anode support for a 4 ⁇ m thick pulsed laser deposition (PLD) formed ESB layer on a GDC layer and (b) its XRD pattern for the as-deposited bilayer sample according to an embodiment of the invention.
- PLD pulsed laser deposition
- Figure 5 shows plots (a) of the I-V characteristics of fuel cell samples at 650 0 C for a
- GDC single-layer and ESB/GDC bilayer electrolytes prepared by PLD of ESB on a cold and on a hot GDC substrate according to embodiments of the invention where the data was collected at 90 seem of air and wet hydrogen and (b) an impedance spectra of the samples having a single and a bilayer electrolyte according to an embodiment of the invention under the same conditions.
- Figure 6 shows backscattered images taken after presintering the AFL at 900 0 C for 1 hour where the porosity and roughness of the (a) rough uncoated anode surface becomes smoother by spray coating a GDC functional layer to (b) a partially GDC AFL coated anode and (c) a fully sprayed GDC AFL coated anode according to an embodiment of the invention.
- Figure 7 shows SEM micrographs of SOFCs fabricated with an AFL according to an embodiment of the invention where (a) is the surface view of the GDC electrolyte deposited by spray coating and (b) is the cross-sectional view of the SOFC with an AFL that is not discernable from the electrolyte after I-V testing.
- Figure 8 shows plots that display the effect of the AFL according to embodiments of the invention on the I-V characteristics and impedance spectra where 30 seem of wet hydrogen and air was used with a) displaying the I-V characteristics for equivalent SOFCs at 650 0 C having no-AFL, a partial-AFL and a complete-AFL and b) displays impedance spectra obtained using two-point probe measurements for the no-AFL, partial-AFL and complete-AFL samples at 650 0 C under open circuit conditions.
- Figure 9 is a plot of the I-V characteristics of a GDC mono-layer electrolyte SOFC having a complete-AFL according to embodiments of the invention at various temperatures ranging from 450 to 650 0 C using 30 seem of wet hydrogen and air.
- Figure 10 shows a) impedance spectra of the sample having a complete-AFL according to embodiments of the invention at various temperatures under operating conditions and b) plots the total, electrode and ohmic ASR values calculated from impedance spectra at temperatures ranging from 450 to 650 0 C using a GDC monolayer electrolyte.
- Figure 11 shows a) the effect of the gas flow-rate on samples having a partial-AFL at 650 0 C that produces 1.03 WcnT 2 when not limited to 30 seem of gas flow-rate and b) the effect of gas flow-rate and gas composition on the performance of a complete-AFL sample at 650 0 C of a GDC mono-layer electrolyte.
- Figure 12 shows a) plots of the I-V characteristics of a Sm x Nd x Ce I-2X Oi -S AFL-free monolayer electrolyte SOFC using 90 seem of wet hydrogen and air at various temperatures and b) ) plots the total, electrode and ohmic ASR values for this monolayer electrolyte calculated from impedance spectra at temperatures ranging from 500 to 650 0 C.
- Figure 13 shows calculated I-V characteristics of a lO ⁇ m DWSB monolayer electrolyte comprising SOFC relative to GDC and YSZ 10 ⁇ m monolayer electrolyte SOFCs at 500 0 C.
- Figure 14 shows a plot of I-V characteristics of three co-pressed samples at 650 0 C using 30 seem of wet hydrogen and dry air for BRO7-ESB and LSCF-GDC composite cathodes and a ESB/GDC bilayer and a GDC single layer electrolyte.
- Figure 15 shows a plot of I-V characteristics of SOFCs with BRO7-ESB composite cathodes and a GDC single layer and a ESB/GDC bilayer electrolyte at 650 0 C made by a colloidal method using 30 seem of air and wet hydrogen, and also for the bilayer electrolyte using 90 seem of wet hydrogen and air flow-rate of 30 seem.
- Figure 16 shows SEM images of PLD formed ESB/GDC bilayer electrolytes according to embodiments of the invention where ESB deposition is on an unheated (a) GDC substrate which is then heated to form a denser layer (b and c) and (d) an ESB layer deposited on a GDC substrate that is heated during PLD.
- Embodiments of the invention are directed to a SOFC where the structure of the electrolyte allows for low temperature ( ⁇ 700 0 C) generation of electricity by a combination of a superior electrolyte structure that has high ionic conductivity and is stable and electrically resistant at low temperatures with a superior anion functional layer (AFL) acting as a triple phase boundary enhancer that couples the electrolyte to the anode.
- AFL superior anion functional layer
- Embodiments of the invention are directed to SOFC with a multilayer structure comprising a porous ceramic anode, an anode functional layer (AFL) to act as triple phase boundary enhancer that couples the electrode to the electrolyte, a bilayer electrolyte comprising a cerium oxide comprising layer and a bismuth oxide comprising layer, an optional cathode functional layer (CFL), and a porous ceramic cathode with low temperature electrical interconnects, where the SOFC displays a very high power density at temperatures below 700 0 C, and as little as about 300 0 C, with hydrogen and/or hydrocarbon fuels.
- AFL anode functional layer
- CFL cathode functional layer
- the low temperature conversion of chemical energy to electrical energy allows the fabrication of fuel cells having stainless steel or other relatively low temperature and inexpensive metal alloys, rather than ceramic conductive oxides, such as Cr-Fe(Y 2 O 3 ), Inconel-Al 2 O 3 or La(Ca)CrO 3 , as the interconnects.
- ceramic conductive oxides such as Cr-Fe(Y 2 O 3 ), Inconel-Al 2 O 3 or La(Ca)CrO 3
- the employment of lower temperatures allows the cell to be more tolerant of any thermal expansion mismatch, to be more easily sealed, to have less insulation, to consume less energy, have a more rapid startup, and to be more stable.
- the bilayer electrolyte comprises a cerium oxide comprising layer and a bismuth oxide comprising layer situated such that the cerium oxide comprising layer is directed toward the anode and sufficiently thick to shield the bismuth oxide comprising layer from the reducing conditions of the anode.
- the bismuth oxide comprising layer is adjacent to the cathode and is greater than or equal to about 1% of the thickness of the cerium oxide comprising layer, for example 60% of the thickness of the cerium oxide comprising layer for a 10 ⁇ m electrolyte for a 500 0 C service fuel cell.
- the actual thickness of the bilayer electrolyte and relative thickness of the layers can vary as necessary for the operating characteristics desired for the specific SOFC application.
- the cerium oxide comprising layer can be, for example, Ce x Sm 1 - x C ⁇ -s (such as (Sm 2 O 3 )Oj(CeO 2 )O 9 ) (SDC), Ce x Gdi -x O 2 - ⁇ (such as (Gd 2 0 3 )o.i(Ce0 2 ) 0 .9) (GDC), or a co-doped cerium oxide, for example, Sm x NdyCe 1 - x .
- x+y Dy x W y O 3 (DWSB).
- the values of x and y can vary considerably, where for mono-doped oxides x or for co-doped oxides x + y is typically 0.1 to 0.35, where the amount of either x or y can be as little as 0.01.
- the values of x and y need not be limited and x and y can range from 0.01 to 0.5 as needed to provide a desired performance and stability as desired by one skilled in the art.
- the GDC or SDC material displays excellent O '2 ion conductivity at low temperatures, but the Ce +4 can be reduced to Ce +3 and allows electrical conductivity causing a leakage current.
- the ESB or other bismuth oxide comprising layer is unstable in a reducing atmosphere and is placed adjacent to the cathode to maintain high O 2 conditions throughout the bismuth oxide comprising layer.
- cerium comprising layers can be substituted for the recited GDC layer and other bismuth comprising layer can be substituted for the ESB layer as can be appreciated by one skilled in the art.
- the anode in an oxidized form can be, for example, NiO-GDC, which can be fabricated, for example, of micron sized NiO particles and submicron sized GDC.
- Anodes comprising other metal oxides such as CuO particles rather than NiO particles can be prepared and used in the SOFCs.
- a GDC or Ni-GDC precursor solution is deposited on the anode surface.
- the GDC precursor solution can be, for example, Gd(NO 3 ) 3 -6H 2 O and Ce(NCb) 3 -OH 2 O and the Ni-GDC precursor solution would also include, for example, Ni(NO 3 ) 3 .
- Nanoparticulate GDC is formed from this precursor solution, which can be applied as an anode functional layer (AFL) to the porous anode to reduce the surface porosity and roughness, yet increases the contact of the NiO with the GDC, as illustrated in Figure 1.
- AFL anode functional layer
- the AFL allows a good contact between the electrolyte and the anode to improve the anodic triple phase boundary.
- a GDC slurry can be coated on the AFL surface, for example by spraying an ethanol suspension, and the composition sintered, for example at 1450 0 C for about 4 hours.
- the AFL increases the effective number of triple phase boundaries where the solid anode, solid electrolyte and gaseous fuel contact, which accelerates the rate of fuel oxidation and the current density of the fuel cell.
- Methods employed to form the AFL according to embodiments of the invention that deposit very fine particles of the cerium oxide comprising layer of the electrolyte suspended in a suspension to form the AFL on the anode are superior to state of the art methods for the formation of AFLs, which have been limited to colloidal deposition of fine powders of the same composition as the bulk anode.
- PLD pulsed laser deposition
- the preferred deposition method employed will depend on the thickness and density of the layer required for a particular SOFC as can be appreciated by one skilled in the art. Deposition methods that can be used include screen printing, spray coating, PLD on a cool substrate and PLD on a hot substrate, which give the least to highest densities of the deposited layer, respectively.
- the second portion of the bilayer electrolyte can be deposited on the GDC electrolyte by, for example, PLD for a dense layer or, alternately, an ESB layer can be screen printed, spin coated, dip coated, spray coated, or drop coated with a colloidal suspension of ESB particles, followed by sintering on the GDC layer.
- PLD has advantages with regard to forming a high density ESB layer with high phase purity and good adhesion to the GDC layer results.
- the ESB layer should be deposited with a sufficient thickness to electrically insulate the cathode from the anode due to the electrical conductance of the GDC layer upon reduction of the Ce +4 in the GDC layer.
- the cathode is deposited on the ESB layer of the bilayer electrolyte.
- Bi 2 Ru 2 O 7 (BR07) powder can be mixed with ESB powder prepared by a solid state route and screen printed on ESB electrolyte as a composite cathode and fired at 800 0 C for 2 hours.
- a cathode such as BRO7 can be deposited on a composite cathode, as shown in Figure 2 for an SOFC having a cathode, bilayer electrolyte, and anode where the bilayer electrolyte and SOFC are relatively thick as co-pressing and screen printing methods were employed for its preparation.
- the SOFC can use, for example, an Er O 8 Bi 1 2 0 3 /Gdo iCeo 9 ⁇ 2 (ESB/GDC) bilayer electrolyte or any other combination that provides higher conductivity and open circuit potential (OCP) than do ceria based electrolytes, such as GDC alone.
- ESD Er O 8 Bi 1 2 0 3 /Gdo iCeo 9 ⁇ 2
- OCP open circuit potential
- GDC open circuit potential
- the interfacial P 02 can be controlled by varying the thickness ratio of the component layers as illustrated in Figure 1.
- ASR total area specific resistance
- pulsed laser deposition can be used to deposit a thin, high-quality bismuth oxide comprising layer, for example an ESB layer on a GDC, or other cerium comprising layer, surface where parameters are set for fast deposition rates with the substrate heated during deposition.
- a high adhesion coefficient is achieved between the GDC surface and a relatively dense crystalline ESB film results.
- the ESB film can be deposited by other means such as screen printing, spin coating, dip coating, spray coating, or drop coating with a colloidal suspension of ESB particles.
- Figure 4a shows a cross-section of an ESB/GDC bilayer electrolyte on Ni-GDC anode support according to an embodiment of the invention.
- the cross-section shows an approximately 4 ⁇ m thick ESB film on a 10 ⁇ m thick GDC layer to yield a 0.4 ESB:GDC thickness ratio.
- Figure 4b shows the XRD patterns for the ESB/GDC bilayer sample. Diffraction patterns for ESB and GDC are visible, due to the large X-rays penetration depth.
- GDC and ESB layers exhibit fluorite structures with slight differences in lattice parameters, such that the reflection lines of the two crystalline structures are grouped in pairs correlating to the same string of Miller indices.
- Figure 4b indicates that a cubic fluorite ESB forms on the GDC layer and suggests an epitaxial grain by grain growth of ESB without an additional heat treatment.
- Figure 5a shows the I-V characteristics of SOFCs having monolayer GDC or bilayer ESB/GDC electrolytes.
- the OCP is 0.72 V and exhibits a maximum power density of 1.03 Wcm "2 at 650 0 C.
- the ASRiv estimated from the initial slope of the I-V curve, is 0.125 ⁇ cm "2 , which is a very low ASR for a SOFC composed of a conventional GDC electrolyte with a LSCF-GDC composite cathode.
- high performance is achieved by a superior SOFC fabrication scheme that employs an improved bilayer ESB/GDC electrolyte and an AFL.
- Figure 5a shows a significant improvement in performance achieved using a bilayer cell over a monolayer GDC cell at 650 0 C.
- the bilayer ESB/GDC electrolyte formed by deposition of an ESB layer on a heated GDC layer and using a BRO7-ESB cathode display an OCP of 0.77 V and a maximum power density of 1.95 Wcm '2 , which is 1.93 times that achieved by the state of the art GDC electrolyte with an LSCF-GDC composite cathode.
- Table 1 indicates that a bilayer electrolyte reduces the total ASR lmpedance of the cell from 0.126 to 0.079 ⁇ cm '2 , resulting from a 48% reduction in the electrode ASR and a 26% reduction in the ohmic ASR.
- the ohmic ASR is lower for the bilayer electrolyte than for the monolayer electrolyte even thought the thickness of the bilayer electrolyte is 1.4 times that of the monolayer electrolyte (4 + 10 ⁇ m vs. 10 ⁇ m). This suggests that the thin bilayer electrolyte prepared according to embodiments of the invention may have ESB penetrating into the GDC grain boundaries to decrease the grain boundary resistances.
- the AFL comprises the same material, for example GDC, as the electrolyte layer adjacent to it.
- the AFL is indistinguishable from the adjacent electrolyte layer in cross-sectional SEM images.
- the formation of the AFL can be viewed during its deposition on the anode's surface.
- Figures 6 shows SEM images of the anode surface before any AFL deposition (a), after deposition of a portion of the AFL material (b), and after complete deposition of the AFL (c), where images of the deposited surfaces were taken after heat treatment at 900 0 C for 1 hour.
- FIG 7 where the surface of anode was spray coated with a GDC electrolyte after the anode has a completely deposited AFL.
- the GDC electrolyte was sintered at 1 ,450 0 C for 4 hours after deposition of the AFL.
- the resultant GDC electrolyte layer is dense.
- the cross-sectional view of GDC electrolyte ( Figure 7b) for the complete- AFL SOFC shows no open porosity in the 10 ⁇ m thick electrolyte layer, yet the high porosity of the anode after reduction of NiO to Ni during operation is apparent in Figure 7b.
- the cell was finished by deposition of a LSCF-GDC composite cathode on the GDC monolayer electrolyte.
- Figure 8a shows the I-V characteristics of this monolayer electrolyte SOFCs where no-AFL, a partial-AFL and a full-AFL were deposited on the anode using 30 seem of wet hydrogen on the anode side and 30 seem of dry air on the cathode side.
- the OCP and the maximum power density of the no-AFL sample were 0.677 V and 407 mWcm "2 , respectively.
- the maximum power density was not high due to the low OCP value.
- the total ASR from the impedance spectrum of the no-AFL sample in Figure 8b was 0.218 ⁇ cm .
- ASR values from I-V and impedance measurements agreed within 10% for all samples. The AFL not only reduces ohmic impedance but also decreases non-ohmic impedance
- the ASR change for the AFL-free, partial-AFL and complete-AFL samples was analyzed by impedance measurements of the three samples where Table 2 gives the total, ohmic and electrode ASR values.
- the AFL-free sample displays a total ASR value of 0.218 ⁇ cm 2 at 650 0 C, where 48% of the total ASR value is from the Ohmic ASR and 52% is from the electrode ASR. Having only a partial-AFL sample reduces the ASR where the measured sample has 59% of the total ASR of AFL-free sample.
- the reduction in the total ASR is due to a 41% reduction in the Ohmic ASR and a 42% reduction in the electrode ASR.
- the ASR difference by use of an AFL is consistent with a difference in the anodic polarization.
- the total ASR was reduced by 60.1% for the sample with a complete AFL relative to that which is AFL-free.
- the total ASR of the sample having a complete-AFL was 0.089 ⁇ cm 2 at 650 0 C resulting in a maximum power density of 994 mWcm "2 , which is a 144% increase relative to that of the AFL-free SOFC of 407 mWcm "2 at 650 0 C.
- the ohmic ASR values decreases 51.0% with this AFL, and the electrode ASR reduces 68.4%.
- cathode polarization is commonly viewed as the dominant contributor to polarization in SOFCs
- removal of more than 60% of the electrode resistance by use of an AFL shows that the dominant electrode resistance can be due to anode polarization for anode-supported cells.
- Figure 9 shows the I-V behavior of a complete-AFL sample at temperatures ranging from 450 to 650 0 C using a monolayer electrolyte.
- the OCP values are 0.796, 0.830, 0.874, 0.913 and 0.950 V at 650, 600, 550, 500 and 450 0 C, respectively.
- the maximum power densities are 994, 913, 627, 440 and 241 mWcm "2 at 650, 600, 550, 500 and 450 °C, respectively for a sample having a 0.49 cm active area where gas flow-rates of 30 seem.
- the I-V curve at 650 0 C shows an increase in ASR with an increase in current density.
- the anode shows concentration polarization at high currents even though large NiO particles were used to enhance anode porosity.
- Figure 10a shows the impedance spectra at each temperature at which I-V was measured for the GDC monolayer electrolyte SOFC.
- Figure 10b shows total, ohmic and electrode ASR values at various temperatures calculated from this impedance data.
- Ohmic and electrode ASR values were obtained from the low and high frequency intercepts of the spectra with the real axis, respectively.
- ohmic and electrode polarization losses are both major contributions to the total cell resistance with electrode resistance from the anode and cathode constitutes 41.38% of the total resistance.
- Electrode resistance increases more than ohmic resistance as the temperature decreases, where at 550 0 C the electrode ASR becomes greater than ohmic ASR.
- electrode resistance becomes 68.79% of the total ASR. However, the total ASR at 500 0 C is still lower than 1 ⁇ cm 2 , resulting in a maximum power density of 440 mWcm "2 . At 450 0 C electrode resistance constitutes 72.64% of the total resistance of the cell.
- FIG. 12a shows I-V characteristics of a Sm x Nd x Ce 1-2X O 2-S monolayer electrolyte without an AFL where a power density in excess of 1.3 W/cm 2 is achieved at 650 0 C with 90 seem of air and wet H 2 .
- Figure 12b the ohmic resistance remains low as a fraction of the total ASR value even at 500 0 C.
- NiO-GDC anode supports were prepared by tape casting a mixture of NiO (Alfa Aesar) and Ceo .9 Gdo .1 O 1.95 (GDC) (Rhodia) powder.
- NiO and GDC powders were mixed (65:35 % by wt.) and ball milled using Solsperse as a dispersant in a mixed toluene/ethyl alcohol solvent for 24 hours.
- a mixture of Oi-n butyl phthalate (DBP), polyethylene glycol (PEG) (plasticizer) and polyvinyl butyral (PVB) (binder) was added to the suspension and the suspension ball milled for 24 hours.
- DBP Oi-n butyl phthalate
- PEG polyethylene glycol
- PVB polyvinyl butyral
- the slurry was transferred to a vacuum chamber and de- aired with constant stirring.
- the slurry was tapecast (Procast from DHI, Inc.) and dried for 2 hours at 100 0 C, and circular green tapes with 32 mm diameter were punched out.
- the circular anode tapes were partially sintered at 900 0 C for 2 hours.
- GDC AFLs were prepared from GDC precursor solutions in ethanol. The solution was transferred to a spray gun (Excell), sprayed onto the anode substrate, and sintered at 900 0 C for 1 hour.
- GDC powder was ball milled for 24 hours using Solsperse in ethanol. PVB and DBP were added and ball-milled was continued for an additional 24 hours.
- Deposition of a GDC electrolyte layer was carried out by spraying the GDC slurry from the spray gun onto the anode or AFL surface and the ceramic placed in a vacuum oven at 120 0 C for 5 hours. The electrolyte coated anode was sintered in air at 3 0 C min "1 to 1,450 0 C and held for 4 hours.
- LSCF Lao . 6Sro .4 C ⁇ o .2 -FeQ . g0 3- ⁇
- ESB was deposited on the spray-coated GDC monolayer using PDL to form an ESB layer of high density.
- the PLD target was prepared by uniaxial pressing of an ESB powder and sintering at 890 °C for 4 hours.
- the ESB powder was prepared by solid state synthesis where erbium oxide (Alfa Aesar) and bismuth oxide (Alfa Aesar) powders were combined in appropriate stoichiometric amounts, ball milled for 24 h and calcined at 800 0 C for 10 hours to yield Er 04 Bi 1 , 6 O 3 .
- a KrF excimer (k 248 nm) laser was used with 5 J cm "2 energy density and 10 Hz frequency.
- the distance between target and substrate was 4 cm, O 2 filling was 0.05 Torr vacuum, and the substrate (GDC surface on NiO-GDC anode) was heated to 600 0 C. Total deposition time was 60 minutes. No additional annealing was applied, and the film was examined by X-ray diffraction (XRD).
- XRD X-ray diffraction
- the composite cathode BRO7-ESB on a bilayer electrolyte where preparation of the cathode layer and the BRO7 was carried out as disclosed in Camaratta et ah, J. Electrochem. Soc. 155 (2008) B 135, incorporated herein by reference.
- Pt paste was brush-painted onto anodes and cathodes as a current collector connected to a Pt mesh and gold lead wires.
- the current collector painted ceramic was heat-treated at 900 0 C for 1 hour.
- Fuel cells were loaded on zirconia tubes in a custom-made testing apparatus using two-part ceramabond sealant (a mixture of 517-powder and 517-liquid from Aremco).
- Dry air and wet hydrogen were supplied to the cathode and anode side, respectively.
- Open circuit potential (OCP) and the current-voltage (I- V) measurements were carried out with Solartron 1287 at various temperatures.
- Total cell ASR (ASRiv) was estimated from the initial slope of the I-V curves.
- impedance analysis were carried out at open circuit conditions using two-point probe measurements with a Par-stat 2273 (Princeton Applied Research) using a frequency range from 10 to 0.01 Hz.
- Impedance spectra were used to calculate the total area specific resistance (ASR lmpe dan cc )- From the high frequency complex plane intercepts of the impedance spectra with the real axis, ohmic ASR values were calculate with resistance normalized according to cathode area. Electrode ASR values were calculated from the difference between low and high frequency intercepts with resistance normalized to the cathode area.
- One method used to fabricate bilayer cells involves co-pressing fine GDC powders onto a composite NiO-GDC anode support.
- the anode support was prepared by uniaxial pressing a well-mixed powder of NiO (Alpha Aesar), a very fine GDC (Rhodia), and a polyvinyl butyral (PVB, Alfa Aesar) binder (3 wt%) in a 1 1/8" cylindrical die at -14 MPa. About 0.35 g de-agglomerated GDC powder was added to the die, being carefully and uniformly spread across the anode substrate surface, and pressed at -42 MPa.
- the pellets were subsequently pressed isostatically at 250 MPa, and sintered at 1450 0 C for 4 h using a 3 °C/min heating rate and a 400 0 C, 1 h binder burnout step to yield a relatively thick electrolyte (-50 ⁇ m).
- An ESB layer was screen printed on top of the sintered GDC layer.
- the ESB powder used in the screen printing ink was prepared by the following solid state technique. Erbium oxide (Alfa Aesar) and bismuth oxide (Alfa Aesar) powders were weighed in stoichiometric amounts, ball milled for 24 h and calcined at 800 0 C for 10 h to yield Er 04 Bi 1 6 O 3 .
- An ESB ink were then prepared by mixing -1 g of the prepared ESB powder (slightly wetted with ethanol) with alpha-terpiniol (Alfa Aesar), di-n butyl phthalate (DBP, Alfa Aesar), and a solution of 10 wt% PVB in ethanol using a 3:1:2 volume ratio in a mortar and pestle until the ink reached a honey-like consistency.
- the ESB ink was screen printed onto the sintered GDC surface and sintered at 890 0 C for 4 h.
- Cathodes of two different composite materials were prepared: 1:1 by weight Lao . 6Sr 0.
- LSCF-GDC cathodes were fired at 1100 0 C for 1 h, and BRO7-ESB cathodes were fired at 800 0 C for 2 h.
- a Pt current collector (Heraeus) was paint brushed onto both electrodes of LSCF-GDC cathode comprising cells and a pure BRO7 current collector that was prepared using the above ink synthesis method was applied to both electrodes of BRO7-ESB cathode comprising cells.
- Lead wires and meshes were attached to the electrodes (using Pt paste on the anode side and the same current collector ink used on the cathode side) and fired in-situ with the testing apparatus.
- Figure 14 shows BRO7-ESB performs better than LSCF-GDC composite cathode on the same GDC electrolyte and that the ESB/GDC bilayer electrolyte was superior to that of the single layer GDC electrolyte.
- the anode support was prepared by tapecasting 65 weight % of NiO (Alfa Aesar) and 35 weight % of GDC (Rhodia) with an appropriate amount of solvents and organic compounds.
- Anode tapes were presintered at 900 0 C for 2 h and GDC electrolytes were deposited by spray coating.
- the increase is not only due to higher OCP but also due to a lower ASR.
- the GDC electrolyte of the bilayer SOFC (20 ⁇ m) was thicker than that for the single layer GDC SOFC by 10 ⁇ m, the I-V curve shows that the bilayer cell exhibits a lower ASR resulting in higher performance.
- the maximum power density increased to 808 mW/cm 2 with the and the ASR decreasing to 0.133 ⁇ cm 2 .
- Table 4 shows results of colloidal deposition of ESB by co- precipitation.
- the bilayer shows a 0.07 V increase in the OCP and a 33 % decrease in the ASR for an improvement of 51 % in the maximum power density.
- Anode supports were prepared by tape casting, as above.
- An AFL was deposited between the GDC electrolyte and the Ni-GDC anode.
- the AFL was prepared by spraying GDC precursor onto a presintered anode and heat-treated at 900 0 C for 1 h.
- For PLD deposition the target was made by uniaxial pressing of ESB powder and sintering at 890 0 C for 4 h.
- ESB powder was prepared by solid state route as above.
- the estimated laser fluence at the target was about 3 J/cm 2 .
- the substrate (GDC surface on a NiO-GDC anode) was maintained at room temperature. The deposition was made for 45 min.
- annealing at 700 and 890 0 C for 4h was employed and the film was imaged by X-ray diffraction (XRD).
- XRD X-ray diffraction
- the crystallinity of the heat-treated ESB layers was compared with the ESB layer without heat treatment. I-V characteristics were measured as described above with 90 seem of dry air and 90 seem of wet hydrogen to the cathode and anode side, respectively.
- Total cell ASR was estimated from the initial slope of the I-V curves, ASRrv- Two-point probe impedance analysis was carried out under open circuit condition using a Par-stat 2273 (Princeton Applied Research) at a frequency range of 10 KHz to 0.01 Hz. Impedance spectra were used to calculate the total ASR (A8Ri mpe dance)- From the high frequency complex-plane intercepts of the impedance spectra with the real axis, the ohmic ASR values were calculated by normalizing the resistance according to cathode area. Electrode ASR values were calculated from the difference between low and high frequency intercepts, normalizing the resistance according to cathode area.
- I-V characteristics were carried out by a Solartron 1287 and the impedance analysis was performed by a Par-stat using 90 seem of air and wet hydrogen.
- ASRiv and ASRi mpe dan c e were used to distinguish the total cell ASR obtained by the two different methods.
- FIG. 16a shows the as-deposited ESB layer on a cool sintered GDC layer was neither dense nor uniform as deposited.
- the poor quality of the ESB layer was not improved after heat treatment yielding a porous and rough ESB layer as can be seen in Figure 16b, although the electrolyte surface is fully covered by ESB with no pin holes through which the underlying GDC electrolyte can be observed.
- the layer is not sufficiently dense to block electronic current from the GDC layer as is suggested from a cross-sectional view, Figure 16c.
- Figure 16d shows that the quality of the ESB film was substantially improved by heating the substrate (GDC electrolyte on the anode) to 630 °C during PLD.
- the ESB membrane thickness was ⁇ 4 ⁇ m achieving a 0.4 thickness ratio of ESB to GDC (GDC electrolyte ⁇ 10 ⁇ m).
- Figure 5a shows the I-V characteristics at 650 0 C of a GDC single layer electrolyte and ESB/GDC bilayer electrolytes where PLD was carried out on a cold and hot GDC substrate.
- the bilayer electrolyte and BRO7-ESB cathode increased the maximum power density from 1.03 to 1.95 W/cm 2 (93 % increase).
- the slope of I-V curves shows that the bilayer electrolyte achieved an ASR of 0.075 ⁇ cm 2 ; a 40 % reduction compared with the single layer sample.
- the increase in OCP from 0.72 to 0.77 V also contributed to the dramatic improvement in power density.
- the OCP of the hot PLD sample, 0.77 V is higher than that of cold PLD sample, 0.71 V. This indicates that the increase in OCP is a function of layer densities and thickness and that PLD deposition on a hot substrate resulted in a dense ESB layer.
- Figure 5b shows the effect of a bilayer electrolyte on ASR measured by impedance spectroscopy, and the values are given in Table 1. Again, the total ASRi mpedance matches well with the ASRjy within 5%. Table 1 shows the reduction in total ASRi mpedance is due to a 48% reduction in the electrode ASR and a 26 % reduction in the ohmic ASR. As was the case for the cold PLD sample, the hot PLD sample also produced lower ohmic ASR than the single layer. The thickness of the GDC layer was ⁇ 10 ⁇ m for both cold substrate and hot substrate PLD deposited electrolytes. However, the reduction in ohmic ASR is more significant in the sample prepared on the cold substrate compared with that of the hot substrate.
Abstract
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KR1020117010093A KR101699091B1 (en) | 2008-10-14 | 2009-10-14 | Advanced materials and design for low temperature sofcs |
US13/124,164 US9343746B2 (en) | 2008-10-14 | 2009-10-14 | Advanced materials and design for low temperature SOFCs |
JP2011532207A JP5762295B2 (en) | 2008-10-14 | 2009-10-14 | New materials and structures for low temperature SOFC |
CA2740293A CA2740293C (en) | 2008-10-14 | 2009-10-14 | Advanced materials and design for low temperature sofcs |
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US10044057B2 (en) | 2011-03-10 | 2018-08-07 | University Of Florida Research Foundation, Inc. | Porous ceramic molten metal composite solid oxide fuel cell anode |
US9252447B2 (en) | 2011-08-25 | 2016-02-02 | University Of Florida Research Foundation, Inc. | Composite anode for a solid oxide fuel cell with improved mechanical integrity and increased efficiency |
WO2015004237A1 (en) * | 2013-07-10 | 2015-01-15 | Danmarks Tekniske Universitet | Stabilized thin film heterostructure for electrochemical applications |
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CA2740293C (en) | 2017-10-03 |
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US20110200910A1 (en) | 2011-08-18 |
JP5762295B2 (en) | 2015-08-12 |
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US9343746B2 (en) | 2016-05-17 |
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