Solid oxide fuel cells conductivity

One leading prototype of a high-temperature fuel cell is the solid oxide fuel cell, or SOFC. The basic principle of the SOFC, like the PEM, is to use an electrolyte layer with high ionic conductivity but very small electronic conductivity. Figure B shows a schematic illustration of a SOFC fuel cell using carbon monoxide as fuel. 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

This presentation reports some studies on the materials and catalysis for solid oxide fuel cell (SOFC) in the author s laboratory and tries to offer some thoughts on related problems. The basic materials of SOFC are cathode, electrolyte, and anode materials, which are composed to form the membrane-electrode assembly, which then forms the unit cell for test. The cathode material is most important in the sense that most polarization is within the cathode layer. The electrolyte membrane should be as thin as possible and also posses as high an oxygen-ion conductivity as possible. The anode material should be able to deal with the carbon deposition problem especially when methane is used as the fuel. 

Double Substitution In such processes, two substitutions take place simultaneously. For example, in perovskite oxides, La may be replaced by Sr at the same time as Co is replaced by Fe to give solid solutions Lai Sr Coi yFey03 5. These materials exhibit mixed ionic and electronic conduction at high temperatures and have been used in a number of applications, including solid oxide fuel cells and oxygen separation. 

Solid mixed ionic-electronic conductors (MIECs) exhibit both ionic and electronic (electron-hole) conductivity. Naturally, in any material there are in principle nonzero electronic and ionic conductivities (a i, a,). It is customary to limit the use of the term MIEC to those materials in which a, and 0, 1 do not differ by more than two orders of magnitude. It is also customary to use the term MIEC if a, and Ogi are not too low (o, a i 10 S/cm). Obviously, there are no strict rules. There are processes where the minority carriers play an important role despite the fact that 0,70 1 exceeds those limits and a, aj,i< 10 S/cm. In MIECs, ion transport normally occurs via interstitial sites or by hopping into a vacant site or a more complex combination based on interstitial and vacant sites, and electronic (electron/hole) conductivity occurs via delocalized states in the conduction/valence band or via localized states by a thermally assisted hopping mechanism. With respect to their properties, MIECs have found wide applications in solid oxide fuel cells, batteries, smart windows, selective membranes, sensors, catalysis, and so on. 

FIGURE 2.7 Change of electrical conductivity at 1000°C with respect to Ni volume content for Ni-YSZ cermets sintered for 2 h at 1200, 1250, 1300, and 1350°C, respectively. (From Pratihar, S.K. et al., Proceedings of the Sixth International Symposium on Solid Oxide Fuel Cells, 99(19) 513—521. Reproduced by permission of ECS-The Electrochemical Society.)... 

Pratihar SK, Baus RN, Mazumder S, and Maiti HS. Electrical conductivity and microstructure of Ni-YSZ anode prepared by liquid dispersion method. In Singhal SC, Dokiya M, editors. Proceedings of the Sixth International Symposium on Solid Oxide Fuel cells (SOFC-VI), Pennington, NJ The Electrochemical Society, 1999 99(19) 513-521. 

Tintinelli A, Rizzo C, and Giunta G. Ni-YSZ porous cermets microstructure and electrical conductivity. In Bossel U, editor. Proceedings of the first European Solid Oxide Fuel Cells Forum. Lucerne, Switzerland European Fuel Cell Forum, 1994 455 164. 

Solid-oxide fuel cell Ion-conducting ceramic (yttrium stabilised zircon oxide) O2- (oxide) 800-1000... 

Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC) The electrolyte and electrode materials in this fuel cell are basically the same as used in the TSOFC. The ITSOFC operates at a lower temperature, however, typically between 600 to 800°C. For this reason, thin film technology is being developed to promote ionic conduction alternative electrolyte materials are also being developed. 

Tubular Solid Oxide Fuel Cell (TSOFC) The electrolyte in this fuel cell is a solid, nonporous metal oxide, usually Y203-stabilized Z1O2. The cell operates at 1000°C where ionic conduction by oxygen ions takes place. Typically, the anode is Co-Zr02 or Ni-Zr02 cermet, and the cathode is Sr-doped LaMnOs. 

High temperature solid oxide fuel cells (SOFCs) have become of great interest as a potentially economical, clean and efficient means of producing electricity in a variety of commercial and industrial applications (Singhal, 1991). A SOFC is based upon the ability of oxide ions to be conducted through a solid at elevated temperatures. Oxide ion conductivity was observed in Zr02 9 mol% YjOj by Nernst as early as 1899. In 1937, Bauer... 

Figure 29. Conductivity of some intermediate-temperature proton conductors, compared to the conductivity of Nafion and the oxide ion conductivity of YSZ (yttria-stabilized zirconia), the standard electrolyte materials for low- and high-temperature fuel cells, proton exchange membrane fuel cells (PEMFCs), and solid oxide fuel cells (SOFCs).

The purpose of the present review is to summarize the current status of fundamental models for fuel cell engineering and indicate where this burgeoning field is heading. By choice, this review is limited to hydrogen/air polymer electrolyte fuel cells (PEFCs), direct methanol fuel cells (DMFCs), and solid oxide fuel cells (SOFCs). Also, the review does not include microscopic, first-principle modeling of fuel cell materials, such as proton conducting membranes and catalyst surfaces. For good overviews of the latter fields, the reader can turn to Kreuer, Paddison, and Koper, for example. 

A solid oxide fuel cell (SOFC) consists of two electrodes anode and cathode, with a ceramic electrolyte between that transfers oxygen ions. A SOFC typically operates at a temperature between 700 and 1000 °C. at which temperature the ceramic electrolyte begins to exhibit sufficient ionic conductivity. This high operating temperature also accelerates electrochemical reactions therefore, a SOFC does not require precious metal catalysts to promote the reactions. More abundant materials such as nickel have sufficient catalytic activity to be used as SOFC electrodes. In addition, the SOFC is more fuel-flexible than other types of fuel cells, and reforming of hydrocarbon fuels can be performed inside the cell. This allows use of conventional hydrocarbon fuels in a SOFC without an external reformer. 

For the purposes of review. Figure 1 illustrates the basic function of the cathode in a solid oxide fuel cell. Whether acting alone or as part of a stack of cells, each cell consist of a free-standing or supported membrane of an oxygen-ion-conducting electrolyte, often yttria-stabilized zirconia (YSZ). Oxygen, which is fed (usually as air) to one side of the membrane, is reduced by the cathode to oxygen ions via the overall half-cell reaction... 

Solid oxide fuel cell (SOFC) working between 700 and 1000 °C with a solid oxide electrolyte, such as yttria-stabilized zirconia (Zr02-8% Y2O3), conducting by the... 

For some applications, such as the cathode materials in solid oxide fuel cells (see Section 5.4.4), a material is needed that can conduct both ions and electrons. The strontium-doped perovskites LaMn03 (LSM), and LaCr03 (LSC) have both these properties. 

A comprehensive analysis of solid oxide fuel cells phenomena requires an effective multidisciplinary approach. Chemical reactions, electrical conduction, ionic conduction, gas phase mass transport, and heat transfer take place simultaneously and are tightly coupled. 

Adler S.B., Wilson J.R., Schwartz D.T. (2003) Nonlinear harmonic response of mixed-conducting SOFC cathodes. In Solid Oxide Fuel Cells VIII (SOFC-VIII), Electrochemical Society Proceedings, 2003-07, S.C. Singhal and M. Dokiya (Eds.), The Electrochemical Society, Pennington, NJ, pp. 516-524. 

Yasuda, I. and Hishinuma, M., Electrical conductivity and chemical stability of calcium chromate hydroxyl apatite, Cas(Cr04)30H, and problems caused by the apatite formation at the electrode/separator interface in solid oxide fuel cells, Solid State Ionics 80, 1995, 141. 

Satisfactory conductivity is maintained up to 1800 °C in air but falls off at low oxygen pressures so that the upper temperature limit is reduced to 1400 °C when the pressure is reduced to 0.1 Pa. A further limitation arises from the volatility of Cr2C>3 which may contaminate the furnace charge. The combination of high melting point, high electronic conductivity and resistance to corrosion has led to the adoption of lanthanum chromite for the interconnect in high temperature solid oxide fuel cells (see Section 4.5.3). 

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