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Annu. Rev. Mater. Res. 2003. 33:91–128 doi: 10.1146/annurev.matsci.33.022802.

091651 Copyright c 2003 by Annual Reviews. All rights reserved First published online as a Review in Advance on February 18, 2003

OXIDE-ION ELECTROLYTES
John B. Goodenough
Texas Materials Institute, Mechanical Engineering, ETC 9.102, University of Texas at Austin, University Station, C2200, Austin, Texas 78712; email: jgoodenough@mail.utexas.edu

Key Words fuel cells, solid oxide, fluorites, perovskites, BIMEVOX, LAMOX s Abstract The performance of the oxide-ion electrolyte of a solid oxide fuel cell (SOFC) is critical to the development of an intermediate-temperature system. Although yttria-stabilized zirconia is the electrolyte used in SOFCs under commercial development, other candidate materials are now available, and there remains a strong motivation to search for new, improved oxide-ion electrolytes. The leading contenders are discussed not only with respect to their oxide-ion conductivity, but also with respect to mechanical and chemical compatibility with the electrodes and the working environment at each electrode.

QUALITY CRITERIA
An electrolyte is an ionic conductor and an electronic insulator. Ideally, an oxideion electrolyte conducts only O2− ions and remains an electronic insulator under operating conditions. Oxide-ion electrolytes are oxides, and the constraints on their ability to remain electronic insulators depend on the application in which they are used. The most stringent application is the solid oxide fuel cell (SOFC) where H2 or a gaseous hydrocarbon fuel is oxidized at the anode (negative electrode) on one side, and gaseous O2 is reduced at the cathode (positive electrode) on the other side. This review evaluates oxide-ion electrolytes for use in SOFCs. In an ideal electrochemical power cell, the ionic current through the electrolyte inside the cell matches an electronic current through an external load. Because ionic conductivities are much smaller than electronic conductivities, the solid oxide-ion electrolyte of a SOFC is in the form of a membrane of small thickness L and large area A that separates electronically the two electrodes of the cell. The internal resistance to the ionic current is R = (L/σo A) + RC + RA , 1.

where σ o is the bulk oxide-ion conductivity of the electrolyte; RC and RA represent, respectively, the resistance associated with the kinetics of reaction at the cathode and anode, including the transfer of O2− ions across the electrolyte
0084-6600/03/0801-0091$14.00

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Figure 1 Typical polarization curve for an electrochemical power cell.

surface. For a current I through the cell, the voltage IR is a potential drop that is to be minimized. Figure 1 illustrates a typical performance (polarization) curve for an electrochemical power cell. The voltage drop η at low currents, region (i), is the total IR drop, which includes the contribution from the kinetics of the chemical reactions at the solid-gas interfaces, whereas the linear drop with increasing current in region (ii) is due to the electrolyte resistance. The final additional voltage drop at high currents, in the diffusion-limited region (iii), is from depletion of acceptor sites or mobile ions at an interface of the cell. A higher σ o on the low-σ o side of the interface displaces region (iii) to higher currents and increases the power density. These simple considerations lead to the following general criteria for the quality of a solid-electrolyte material to be used in an electrochemical cell: (a) Ease of fabrication into a mechanically strong membrane of small L and large A to minimize (L/σ oA) in Equation 1. Optimization of cell design may also require the fabrication of membranes of complex shape. (b) Even with a small L/A ratio, an oxide-ion conductivity σ o > 10−2 S/cm at the cell-operating temperature Top is required. Note: In general, the conductivity is a tensor; but for polycrystalline electrolytes, a scalar σ o is used. However, for tunnel or layered structures having ionic conductivity in only one or two dimensions, it is necessary to appreciate that σ = σ⊥ , so the scalar σ o measured on a polycrystalline sample may be reduced significantly from the conductivity in the optimum direction within an individual grain.

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(c) Low resistances RC and RA to reduction and oxidation of the reactants and O2−-ion transfer across the electrolyte/gas or electrolyte/electrode interface. The surface reactions may take place at a catalytic electrode, but transfer of O2− ions must still take place across an electrolyte/gas or electrolyte/electrode interface, so chemical and mechanical compatibility of the electrode/electrolyte interfaces is an important aspect of the electrolyte properties. The formation of blocking interface phases must be avoided. (d) Retain a negligible electronic conductivity σ e at Top under operating atmospheres, i.e., retain a transport number to = σo /σ ≈ 1, 2.

where the total conductivity is σ = σ o + σ e if the O2− ions are the only mobile ions. (e) Chemical stability in the working environment, which includes reactions at electrode/electrolyte as well as reactant/electrolyte interfaces. Thermodynamic stability vis a vis the reactants is achieved only by placing the bottom ` of the electrolyte conduction band above the highest occupied molecular orbital (HOMO) of the reductant and the top of the electrolyte valence band below the lowest unoccupied molecular orbital (LUMO) of the oxidant as illustrated in Figure 2. Note: The Fermi energies of the metallic electrodes

Figure 2 Placement of reactant energies relative to the edges of the electrolyte conduction and valence bands in a thermodynamically stable electrochemical cell at flat-band potential.

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should also lie in the energy gap Eg of the electrolyte, with that of the anode rising to the HOMO of the reductant and that of the cathode falling to the LUMO of the oxidant under operating conditions. (f) Mechanical stability against thermal cycling between ambient temperature and Top requires matching of thermal-expansion coefficients of the electrolyte and electrodes, the interconnects, and the seals. Note: Ceramic strength is improved where cell design retains the ceramic membrane under a compressive stress. (g) Costs of material and fabrication as well as operational life are always considerations. Given these quality criteria, the challenge is to design a material that meets all of these demands on a solid oxide-ion electrolyte operating at a temperature Top < 800◦ C. In order to meet this challenge for a SOFC, it is necessary first to understand how the constraints imposed by these quality criteria limit the choice of materials.

ELECTRONIC ENERGIES
Electronic energies determine the electrolyte window, i.e., the edges of the conduction and valence bands of an electrolyte relative to the HOMO and LUMO of the reactants. Oxide-ion conductors are oxides, and oxide-ion electrolytes are considered ionic compounds. Therefore, it is appropriate to start construction of electronic energy-level diagrams from the constituent ionic energies rather than from atomic energies. Figure 3 illustrates such a construction for the electronic and

Figure 3 Construction of conduction and valence bands of MgO with an ionic model.

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ionic insulator MgO. The energies of the redox couples Mg2+/Mg+ and O−/O2− relative to the bottom of the vacuum energies, (designated Vac in Figure 3) are given by the ionization potential of Mg+ and the electron affinity of O−. EI represents the total energy required to move an electron from the Mg+ ion to an O− ion at infinite separation, thereby creating free Mg2+ and O2− ions. The energy EM is the electrostatic Madelung energy gained by arranging point charges 2+ and 2− at the Mg and O positions of the MgO rock-salt lattice. The internal crystalline electric field conserves the total energy and inverts the relative energies of the Mg2+/Mg+ and O−/O2− couples provided the condition EM > EI is met. Overlap of the empty Mg–3s orbitals on neighboring Mg2+ ions and of filled O–2p orbitals on neighboring O2− ions broadens the redox energies into itinerant-electron states of a conduction and a valence band, respectively. Although some back-transfer of electronic charge from the O2− to the Mg2+ ions gives a polarization correction that reduces the effective ionic charges, the resulting reduction in EM is largely compensated by the quantum-mechanical repulsion between the Mg–O antibonding states of the conduction band and the bonding states of the valence band. Therefore, the introduction of a covalent contribution to the bonding introduces Mg–3s and 3p character into the O–2p states of the valence band and O–2p character into the conduction band, but it scarcely alters the mean energies of these bands. In MgO, an energy gap Eg ≈ 7.5 eV separates the filled valence and empty conduction bands of bonding and antibonding states. Figure 4 shows a similar ionic-model construction of the electronic energies for the isostructural transition-metal oxide MnO. In this case, the crystalline electric

Figure 4 Construction of Mn:3d5 localized-electron configuration relative to conduction and valence bands in MnO with an ionic model.

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fields responsible for EM also lift the Mn:3d5 level above the top of the bonding O–2p valence bands. In this schematic diagram, the conduction and valence bands consist of itinerant one-electron states, but the 3d5 level is a localized multielectron level corresponding to a redox couple such as that found in an aqueous solution of Mn2+ ions. The designation N(E) for the density of one-electron states applies only to the conduction and valence bands; however, the redox couple contains one state per Mn atom and can be incorporated into the same electronic energy diagram. Oxidation of MgO requires oxidation of the O–2p valence band and therefore a lowering of the Fermi energy EF (the electrochemical potential) down into the valence band. The creation of peroxide ions lifts the empty antibonding bands of a peroxide ion (O2)2− well above the top of the O–2p bands, but the peroxide ion is formed only with large, electropositive cations such as Ba2+, where the additional oxygen forms part of their nearest-neighbor coordination. Even where the cations lack their full complement of O2−-ion nearest-neighbors, as occurs at an oxide surface or with a large cation as in the case of BaO, it is energetically more favorable to introduce the oxygen of a water or a CO2 molecule than to create peroxide ions; BaO converts rapidly to Ba(OH)2 and then to BaCO3 on exposure to ambient air, whereas oxides having a full nearest-neighbor O2−-ion configuration at the bulk cations may only bind water at the surface. Nevertheless, large surface cations like Sr2+ or Ba2+ of a perovskite may attract CO2 to form unwanted carbonates at an oxide surface. On the other hand, oxidation of MnO requires only lowering of EF into the 3d5 redox couple, so diffusion of manganese from MnO into an adsorbed O2 layer at the surface on the cathode side can create Mn3+ ions and introduce electronic conductivity in a mixed-valent Mn3+/Mn2+ couple. The layered oxides La2NiO4 and La2CuO4 represent an interesting special case. These oxides have the layered K2NiF4 structure in which two (LaO)+ rock-salt sheets alternate with a (NiO2)2− or a (CuO2)2− sheet. Although their Ni3+/Ni2+ or Cu3+/Cu2+ redox couples are pinned at the top of the O–2p bands, nevertheless they can be oxidized to metallic La2NiO4+δ and La2CuO4+δ by the introduction of interstitial oxygen between the two LaO sheets of a rock-salt layer. These interstitial oxygen are mobile at room temperature, whereas oxygen vacancies in oxides tend to move with an activation energy Ea > 0.6 eV. From the construction of Figures 3 and 4 and the above discussion, it follows that a large electrolyte stability “window” Eg and stability against oxidation not only requires an oxide with a large energy difference EM − EI and a structure containing bulk cations with a full O2−-ion coordination, but also the absence of any cationic dn of fn redox energies between the top of the O–2p valence bands and the HOMO of the fuel. Therefore, oxide-ion electrolytes appear to be confined to oxides of the main-group elements, Zr(IV) and Hf(IV) of the d-block transition metals, and lanthanides that do not have a 4fn energy lying within the gap Eg. Moreover, the heavier main-group elements Sn, Sb, Tl, Pb, and Bi have outer 5s or 6s states that are too stable to give a large enough Eg. Nevertheless, CeO2-based electrolytes having a localized Ce:4f1 energy level in the gap Eg between the Ce-5d conduction

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band and the O–2p valence band are under development as a solid electrolyte because the polaronic conduction associated with a Ce4+/Ce3+ couple is diffusive with an activation energy that may render tolerable the electronic conduction. The Bi(III)/6s2 core electrons are stabilized sufficiently to resist oxidation in an air atmosphere, but Bi(III) is reduced in an H2 atmosphere. In the oxides with a large Eg and no redox energy within Eg, aliovalent cation substitutions are generally charge-compensated by the introduction of native defects, e.g., an oxygen vacancy in Zr1−xCaxO2−x. However, where an oxygen vacancy creates too small an oxygen coordination at a cation, as occurs in the brownmillerite Ba2In2O5, then water may be inserted into the vacancies to create OH− ions; in this case, the oxide becomes a protonic electrolyte rather than an oxide-ion electrolyte at the lower temperatures where the water is retained. Moreover, the introduction of too many oxide-ion vacancies may result in the formation of vacancy-ordered clusters that trap out the mobile vacancies. These complications together with a charge q = −2e at an oxide ion have made difficult the identification of a fully satisfactory O2−-ion electrolyte for use in a SOFC operating at temperatures Top < 800◦ C.

IONIC ENERGIES Intrinsic Ionic Energy Gap Hg

At ambient temperatures, oxygen-stoichiometric oxides have arrays of crystallographically equivalent, and therefore energetically equivalent sites completely filled with oxide ions. We designate these sites as normal in order to distinguish them from interstitial sites,which have a higher ionic potential energy. The highest normal-site ionic energies are separated from the lowest interstitial-site energies by an energy gap Hg, as is illustrated in Figure 5; this ionic energy gap is analogous to the electronic energy gap Eg of an electronic insulator. No ionic conduction is possible on the normal sites if they are all filled, and there are no mobile ions in

Figure 5 Energies of a working ion in a stoichiometric ionic compound (black circles indicate an occupied site).

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the interstitial sites if they are all empty. In most ionic solids, Hg is not strongly temperature-dependent below the sintering temperature where ionic diffusion occurs; significant ionic conduction requires near-sintering temperatures to excite ions from normal to interstitial positions, and this ionic disorder lowers Hg to introduce a positive feedback for ionic excitation. On the other hand, there are stoichiometric solids having an array of partially occupied atomic sites that become crystallographically and energetically inequivalent only because of atomic ordering within the array. For example, the zinc-blende structure of ZnS has anions ordered into half the tetrahedral sites of a face-centeredcubic cationic array, whereas the fluorite structure has all the tetrahedral sites occupied. We may, therefore, imagine a situation where the anions of a zinc-blende structure become disordered above a transition temperature of the solid. This situation is illustrated schematically in Figure 6. In the ordered zinc-blende structure, the ionic potential energy of the empty sites is at an energy Hg above that of the occupied sites; but in the disordered anion-deficient fluorite structure above Tt, the sites are crystallographically equivalent and the potential energies of the empty and occupied sites would effectively differ only by the motional enthalpy Hm required to move an anion from an occupied site to a crystallographically equivalent empty site. The energy gap Hg becomes strongly temperature-dependent as the temperature increases to Tt, vanishing for T > Tt. Consequently, a transition from a poor to a fast anion conductor would occur at Tt, and this transition may be first-order. The order parameter for the order-disorder transition can be defined as Hg(T)/ Hg(0), the ratio of the gap at temperature T to its value at T = 0 K. At temperatures T < Tt, the fraction of normal sites that are vacant is nv ∼ exp(− Hg /kT), 3.

and the fraction of the interstitial sites that are occupied is mnv, where m = 1 in the case of 50-50 occupied and vacant sites in the disordered array. The fraction of mobile vacancies on the total number of crystallographically equivalent sites in the disordered array is (1 + m)−1. In Figure 6, the presence of short-range order above Tt is signaled by a Hg(T)/ Hg(0) that remains finite for a temperature interval above Tt.

Motional Enthalpy

Hm

Oxide ions move diffusively where they partially occupy an array of crystallographically equivalent sites. Figure 7 illustrates the variation of the ionic potential with position for three situations in which ions partially occupy a set of energetically equivalent sites. The partially occupied sites may share common faces in a continuously connected network through the structure as illustrated schematically in Figure 7a. On the other hand, they may be separated from one another by an array of empty sites with which they share a common face, e.g., by empty tetrahedral sites of a face-centered-cubic array with edge-shared octahedral sites that

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Figure 6 Top: Ionic energies (black circles indicate occupied sites) for ordered and disordered partial occupation of a set of sites that are crystallographically equivalent if ions are disordered. Bottom: Order parameter and Arrhenius plots for smooth versus first-order transitions.

are partially occupied, Figure 7b, or they may be separated from one another by a filled array of sites with which they share common faces, Figure 7c, where mobile ions occupy the filled array. In all three cases, the common site faces act as a barrier for the ionic motion. In order for an ion to pass through such a face, or bottleneck, the shortest distance Rb from the center of the face to a peripheral ion must be large enough to allow it to pass. Where Rb is less than the sum of the radii of the mobile and peripheral ions, thermal energy must be supplied to open up the face; where Rb is larger

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than the sum of the ionic radii, thermal energy may need to be supplied to move the mobile ion away from a site on the side of the free volume into the center of the open channel. Even where Rb is roughly equal to the sum of the ionic radii, some thermal energy must be supplied to excite the mobile ion to the maximum in the potential-energy curve at the saddlepoint position in the center of the face. The energy for an ionic jump from a filled to an empty site is the motional free energy Gm = Hm − T Sm. The motional enthalpy Hm = Hb + Hr 4.

has two components, a barrier energy Hb for the ion to hop when the acceptor and donor sites have the same potential energy and a relaxation energy Hr that must be supplied to make equal the donor and acceptor potential energies. Hr is present because the time it takes for the mobile ion to hop over the barrier Hb is longer than the time it takes for the host matrix to relax the metal-oxygen bond lengths at the occupied sites to their equilibrium value at the expense of the ionic potential of the empty sites. Hb is minimized by matching the mobile-ion size to Rb, and Hr by matching the mobile-ion size to the equilibrium metal-oxygen bond length when the ion is at the center of the site. These two conditions are incompatible with one another, and the lowest value of Hm for O2−-ion conduction is found where the peripheral cations of the bottleneck are easily polarized, as is the case with the 6s2 core of the Bi3+ ion. Where the partially occupied sites are separated by inequivalent sites as in Figures 7b,c, fast ionic motion requires that the mobile-ion potential at the intervening sites be nearly the same as that at the partially occupied sites. From the constructions of Figure 7b, it is apparent that the electrostatic forces between the mobile ions tend to smooth the potential where the inequivalent sites are filled with mobile ions, whereas the local relaxation energy Hr may enhance the potential-energy difference of the inequivalent sites where they are empty.

Trapping Energy

Ht

Where the normal sites are fully occupied, oxygen vacancies or interstitials may be created by the substitution of aliovalent cations. In the stabilized zirconia Zr1−xCaxO2−x, for example, the substitution of Ca2+ for Zr4+ not only stabilizes the fluorite structure, it also introduces oxygen vacancies to compensate for the smaller charge on the Ca2+ ion. Although the creation of oxygen vacancies by aliovalent doping is analogous to the introduction of holes into the valence band ←− − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − −− Figure 7 (a) Definition of bottleneck shortest distance Rb and variation of mobile ion position with (solid line) and without (dotted line) relaxation of host structure. (b) Variation of mobile ion potential energy for occupied sites separated by an array of inequivalent empty sites. (c) Smoothing of the potential of (b) by the introduction of mobile ions into the intervening array of sites.

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of silicon by doping with boron, the trapping energy of an oxygen vacancy at a dopant is greater than the trapping of a hole at an acceptor site in silicon. In the case of an acceptor site in silicon, a hydrogenic model is appropriate; in this case, both the kinetic and the potential energies of the trapped hole are included, and the screening of the coulombic attraction by the dielectric constant κ > 10 reduces the binding energy by a factor κ −2, which reduces the trapping energy of a hole to an (EA−EV) < 0.1 eV. In an ionic conductor, on the other hand, only the potential energy is to be considered, so the dielectric screening reduces the coulombic contribution Hc to the trap energy by only a factor of κ −1, which makes 0.1 < Hc < 1 eV. In addition, an ionic dopant of different size also creates a local elastic strain that may attract the mobile species with an additional relaxation energy Hr, so the total trapping energy is Ht = Hc + Hr . 5. Substitution of a larger Ca2+ ion for Zr4+ in stabilized zirconia, for example, creates a local elastic strain field that also attracts the oxygen vacancy to the dopant Ca2+ ion (1, 2). In order for the oxygen vacancy introduced by doping to contribute to a dc conductivity, it must either free itself from the dopant or find a tortuous percolation pathway through the solid via dopant nearest-neighbors. However, doping heavily enough to provide such percolation pathways tends to make the oxide metastable with respect to segregation of an ordered-vacancy phase, and operation at higher temperatures can lead to the phenomenon of aging, in which the mobile-ion vacancies become trapped in clusters. Aging can be a problem in the stabilized zirconias where relatively heavy doping is required to stabilize the fluorite structure.

IONIC CONDUCTIVITY Phenomenology
In a crystal, the electronic and ionic conductivities are generally tensor quantities relating the current density j to the applied electric field E in accordance with Ohm’s law. In an isotropic medium such as a cubic crystal or a polycrystalline ceramic, the conductivity σ is a scalar, and Ohm’s law has the form for oxygen-vacancy conduction jo = σo E = nv N qvo , 6. where N is the number of normal sites per unit volume, q = 2e is the lattice charge of the oxygen vacancy moving with velocity vo, and nv is the fraction of sites that are vacant. From the definition of charge-carrier mobility uo ≡ vo/E, the oxygen-vacancy conductivity is σo = nv N quo . 7. The Nernst-Einstein relationship between the ionic diffusion coefficient D = Doexp(− Gm/kT) and the mobility is

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u = qD/kT, and substitution of Equation 8 into Equation 7 gives σo = (A/T ) exp(−E a /kT), where, for a temperature-independent nv, Ea = Hm ,

9.

10. 11.

A = (N q2 /k)nv Do exp( Sm /k).

The theory of random walk, which neglects correlated ionic motion, is used to obtain a general expression for Do. Because two atoms cannot occupy the same site, the transition probability for a vacancy to move to a neighboring site is z(1 − nv)fυ(E), where (1 − nv)z is the probability of finding an O2− ion on the z near-neighbor sites, and f is a geometrical factor of order unity that depends on the jump path. The jump frequency υ(E) = υo exp(− Gm /kT) 12.

contains the attempt frequency υ o of the mobile oxide-ion optical-mode vibrations (1012–1013 Hz). In an electric field, E, the enthalpy Hm − (qE · l/2) for jumps in the direction of the field is lower than the Hm + (qE · l/2) for jumps in the opposite direction, where l is the vector measuring the distance between neighboring sites; l/2 is the vector distance to the saddlepoint between sites. The net drift velocity vx in the direction lx is the product of (lx/2) and the difference in the jump probabilities in the forward and back directions. Because qE · l/2 kT holds at temperatures where the ions are mobile, it follows that
2 vx ≈ (qEx /kT) lx /2 z(1 − nv ) fυ,

13.

2 2 2 where υ = υ(E = 0). For an isotropic medium, lx = ly = lz allows replacing 2 2 lx /2 by l /6 and from Equation 8 with ux = Ex/vx,

D ≈ (l 2 /6)z(1 − n v ) fυ. Equation 11 then becomes A = γ (Nq2 /k)nv (1 − nv ) l 2 υo , γ ≈ f(z/6) exp( Sm /k)

14.

15. 16.

for three-dimensional conduction. For 2D or 1D conduction, σ⊥ and σ || have z/6 → z/4 and z/2, respectively, in Equation 16. In a stoichiometric material at T < Tt, an nv ∼ exp(− Hg/2kT) introduces an additional term into the activation energy Ea of Equation 10: Ea = Hm + ( Hg /2), 17.

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providing Hg is temperature-independent. As T increases to a Tt, Hg becomes temperature-dependent, which increases the pre-exponential term A and the apparent value of Ea, as is illustrated in Figure 6. A measurement of log(σ oT ) versus (1/T) over a finite temperature interval that gives a value of A significantly greater than the value obtained from Equation 15 signals a Hg = Hg(T ). In a doped material, the trapping energy Ht adds to the activation energy Ea of Equation 10, which becomes Ea = Hm + ( Ht /2). 18.

From these simple phenomenological considerations, it is clear that two dominant considerations in the design of a solid electrolyte are the creation of a temperature-independent nv(1 − nv) > 0 and a minimization of the activation energy Ea.

Correlated Ionic Movements
In the random-walk model, the individual ions are assumed to move independently of one another. However, long-range electrostatic interactions between the mobile ions make such an assumption unrealistic unless nv is quite small. Although corrections to account for correlated motions may be expected to alter only the factor γ of Equation 15, the situations represented by Figure 7b,c need to be considered explicitly. In the case of Figure 7b, a small Hm for a cooperative cluster rotation to the intervening sites (or saddlepoint positions) may lower the energy for excitation to the intervening sites, thus effectively introducing a Hg(T ) that collapses in a smooth transition. At temperatures T > Tt, the mobile ions become disordered over the normal and interstitial (or saddlepoint) sites. Such a situation appears to be illustrated by the stoichiometric fluoride-ion conductor PbF2, which has the fluorite structure (3). The situation illustrated in Figure 7c illustrates the displacement of mobile ions from intervening filled sites by a mobile ion where a smoothing of the ionic potentials makes those at the filled sites nearly the same as those at the normal sites. This situation has been identified (3) in the fast Na+-ion conductor Na1+3xZr2(P1−xSixO4)3. Condensation of disordered vacancies into ordered clusters may transform correlated motion to single-vacancy diffusion of the mobile vacancies.

ILLUSTRATIVE OXIDE-ION ELECTROLYTES
Although there are several candidate oxide-ion electrolytes, none is completely satisfactory for SOFCs with a Top ≤ 800◦ C. They fall into a few structural categories, but in each, oxide-ion conduction is by oxygen vacancies. The different problems encountered with these candidates are illustrative of the challenges facing the designer of an oxide-ion electrolyte.

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Oxides with Fluorite-Related Structures
The discovery by Faraday of fast F−-ion conduction in stoichiometric PbF2 signaled that the fluorite structure is capable of conducting anions. However, no comparable AO2 oxide exists because there is no stable A4+ cation with a 6s2 lone pair; there is only the high-temperature δ-Bi2O3 phase containing Bi3+:6s2. Therefore, early attempts to obtain a fast oxide-ion conductor concentrated on aliovalent doping on the A sites of AO2 oxides so as to introduce oxygen vacancies, or on substitution for Bi in Bi2O3 so as to retain the δ-Bi2O3 structure to room temperature. These studies were extended to the fluorite-related pyrochlore structure containing an ordered array of 0.5 A3+ + 0.5 B4+ cations.
STABILIZED ZIRCONIA High-temperature zirconia (ZrO2) has the cubic fluorite structure of Figure 8; on cooling from its melting point (2680◦ C), it transforms to a tetragonal form at 2370◦ C and then to a monoclinic form at 1170◦ C. The high-temperature structure can be stabilized to room temperature by substitution of larger cations of lower valence (e.g., Zr1−xCaxO2−x or Zr1−xYxO2−0.5x) for Zr4+, which also introduces oxygen vacancies on the normal sites and therefore oxide-ion conductivity. If the dopant content is not sufficient to fully stabilize the cubic structure, then the material may consist of two or more phases. The amount of dopant required to fully stabilize the cubic structure is about 12–13 mol% for CaO, 8–9 mol% for Y2O3 and Sc2O3, and 8–12 mol% for other rare-earth oxides (4). The tetragonal phase is stabilized with a low-dopant content, i.e., about 2 to 2.5 mol% for Y2O3 and several other rare-earth oxides (5). The cubic phase has low strength, toughness, and thermal shock resistance, whereas the tetragonal phase has extremely high strength and toughness due to a stress-induced phase transformation to monoclinic zirconia. However, the tetragonal phase is unstable in a moist environment. Compositions containing 3 to 7 mol% Y2O3 or Ln2O3 (Ln = Nd, Er, Yb, Sm) segregate into the cubic and tetragonal phases if

Figure 8 The cubic fluorite structure of CaF2 or CeO2.

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slow-cooled, but form a tetragonal t -phase with tweed-like microstructure if quenched from the sintering temperature (5). The t -phase segregates to a dopant-rich cubic phase and a low-dopant tetragonal phase on heating in the range 800 < T < 1200◦ C (6). Where phase segregation occurs, the mobile oxygen vacancies become trapped out in the non-percolating phase, which makes the conductivity decrease with time. All compositions below 8–9 mol% M2O3 dopant show the aging phenomenon, and the highest conductivity is with about 9 to 10 mol% M2O3 as dopant. Of all the stabilized zirconias, Sc2O3 gives the highest value of σ o as the size of the Sc3+ ion is most closely matched to that of Zr4+, and it has only a single difference in charge, which minimizes both Hc and Hr in Ht of Equation 5. However, cost considerations make Y2O3 the stabilizer of choice. In various zirconia-based systems having no impurity phases formed in grain boundaries, a change in the slope of the Arrhenius plots of log(σ oT ) versus 1/T is consistently observed near 800◦ C; a higher activation energy Ea is observed at lower temperatures, and the low-temperature value of Ea increases with dopant concentration (4). This behavior is characteristic of dopant ions acting as nucleating centers for the formation of ordered-vacancy clusters. The simplest model for such a condensation consists of nucleation centers having a critical temperature T ∗ below which the oxygen vacancies are progressively trapped out into the clusters with decreasing temperature; above T ∗ , the vacancies are dissolved into the matrix of oxygen sites. A formal treatment of this model is similar to that for dissolution of a solid into a liquid solvent. If the chemical potentials of the condensate and the solid solution with a random distribution of vacancies are µ∗ (cond) and µ∗ (sol), v v respectively, then at equilibrium µ∗ (cond) = µo (cond) = µo (sol) + kT ln(nv /n∗ ), v v v v 19.

where n∗ is the total fraction of oxygen sites that are vacant in the absence of a v condensate and nv/n∗ is the fraction of oxygen vacancies that are dissolved into v random positions on the oxygen-atom sublattice. At temperatures T < T ∗ , the free energy for trapping vacancies into clusters is Gt(T ) = µ∗ (cond) − µ∗ (sol). v v Because Gt(T ∗ ) = 0 and the standard states of the disordered and ordered phases are the same, it follows that ln(nv /n∗ ) = (− Ht /kT)[1 − (T /T ∗ )], v 20.

provided H and S for the condensate are independent of temperature and Ht = T ∗ St. Combining Equation 20 with Equations 9 and 15 gives, for n∗ 1, v ln(σo T) = ln A − (Ea /kT), A ≈ γ (Nq2 /k)n∗l 2 υo , v where for T < T ∗ , Ea = Hm + Ht [1 − (T /T ∗ )], 23. 21. 22.

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and for T ≥ T ∗ , Ea = Hm . 24.

It follows that an Arrhenius plot would give two straight lines intersecting at T ∗ with activation energies E1 = Hm and E2 = Hm + Ht with pre-exponential terms A1 = A and A2 = A exp( Ht/kT∗ ), respectively; and at T = T ∗ , ln(A2 /A1 ) = Ht /kT∗ = (E 2 − E 1 )/kT∗ . 25.

An expression similar to Equation 25 was also derived by Nowick et al. (7) and one similar to Equation 23 was given by Kilner & Waters (8), who attributed trapping of the oxygen vacancies at the dopants that introduced them. In summary, yttrium-stabilized cubic zirconia has an acceptable oxide-ion conductivity σ o at temperatures T > T ∗ ≈ 800◦ C provided thin (L ≤ 20 µm), dense ceramic membranes can be fabricated free of grain-boundary impurities and the dopant concentration is kept in the range 9 to 10 mol% Y2O3 at the edge of the cubic-phase domain. Smaller dopant concentrations are plagued by aging; higher dopant concentrations encounter formation of ordered-vacancy phases. Although the sintering temperatures of zirconia are high (near 2000 K), the zirconias are chemically inert to the gaseous reactants of a SOFC and to most of the preferred electrode materials, which is why it is the electrolyte of choice for the majority of efforts to realize a commercially viable SOFC. However, a word of caution is in order. If the cathode contains La, then fabrication at temperatures above 1200◦ C introduces a La2Zr2O7 pyrochlore phase at the electrode/electrolyte interface that blocks O2−-ion migration across the interface. Eyring (9) has summarized the phase-diagram studies of the rareearth binary oxides having a fluorite-related structure. Cerium, praesodymium, and terbium may be oxidized to RO2 with the fluorite structure. However, the Pr3+;4f2 and Tb3+:4f8 redox energies lie in the energy gap Eg between a R-5d conduction band and the O–2p valence band at an energy close enough to the top of the valence band that PrO2 and TbO2 are easily reduced to RO2−x, 0 ≤ x ≤ 0.5. The Ce3+:4f1 level is less stable, but it also lies in the gap Eg, and CeO2 is reduced to CeO2−x in the reducing atmosphere at the anode of a SOFC. The formal lattice charge at an oxygen vacancy is 2+, and the nearest-neighbor metal atoms tetrahedrally coordinated to an oxygen vacancy move away from the vacancy; the neighboring oxygen atoms move toward it. These atomic displacements give a relaxation enthalpy Hr that destabilizes the oxide-ion potential at the vacancy site. The vacancy also traps the two electrons it introduces as localized 4f1 configurations at neighboring Ce3+ ions; these electrons move as small polarons once freed from a trap site neighboring a vacancy. A general feature of oxygen-deficient RO2−x fluorite-related structures is ordering of the oxygen vacancies at lower temperatures within slabs that alternate with RO2 slabs. A common feature of the vacancy-rich slabs is an ordering of
DOPED CERIA

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oxygen-vacancy pairs across the diagonal of an elementary simple-cubic complex of the face-centered-cubic array. In order to introduce oxygen vacancies into ceria without reducing the cerium to Ce3+, a rare-earth R3+ ion having no 4fn level in the gap between Ce-5d and O–2p bands is substituted for Ce in Ce1−xRxO2−.0.5x (10). Although this strategy gives a transport number to ≡ σ o/σ ≈ 1 in air or an inert atmosphere such as argon, Ce3+ ions are created in a reducing atmosphere to give a measurable electronic component σ e in the total conductivity σ = σ o + σ e. The electronic component is a polaronic charge transfer 4f1 to 4f0 on the mixed-valent Ce4+/Ce3+ array. In a ceramic membrane, the resistivity ρ o = ρ b + ρ gb to oxide-ion conduction contains two components: an intragrain (bulk) resistivity ρ b and a grain-boundary resistivity ρ gb that can be distinguished in ac-impedance data, but not in a dc measurement. Huang et al. (11) have measured the ac-impedance of a dense ceramic membrane of Ce0.9Gd0.1O1.95−δ in different atmospheres. In air and argon, the transport number is to ≈ 1, i.e., δ ≈ 0, and Figure 9 compares σ o(total) with σ o(bulk) as measured in air. Whereas σ o(total) shows a nearly linear Arrhenius plot with little curvature in agreement with dc measurements (12–14), the bulk conductivity σ o(bulk) exhibits a marked curvature indicative of a temperature-dependent Ea(bulk). A temperatureindependent Ea(grain boundary) masks the temperature dependence of Ea(bulk) in the Arrhenius plot of σ o(total). In the doped-ceria systems, the dopant ions may not act simply as traps for isolated oxygen vacancies, but also as nucleating centers for the formation of ordered-vacancy clusters. The inset of Figure 9 shows a fit of Equations 21–24 to the Arrhenius plot for σ o(bulk) with a T ∗ = 583 ± 45◦ C, Hm = 0.63 ± 0.01 eV and Ht ≈ 0.19 ± 0.01 eV = 2.57 kT∗ . A measured Ht > kT∗ probably reflects the presence of short-range order among the disordered vacancies, which would increase the effective Hm and therefore introduce a curvature in ln(σ oT ) versus 1/T above T ∗ . The measured curvature at T ≥ T ∗ may also reflect the neglect of (1 − nv) with different nucleation temperatures resulting from the random distribution of dopant ions. Although no attempt was made to refine the simplified model that yielded Equations 21–24, it was noted that heavy doping creates a segregation into vacancy-ordered and -disordered phases; in this case, the vacancies appear to move in percolation pathways. At these doping levels, experimentation (12) indicates little curvature of the plot of ln(σ oT) versus 1/T, which is similar to the grain-boundary contribution to the resistance. The bulk electronic conductivity found in a reducing atmosphere for Ce0.9Gd0.1 O1.95 is given by σe = σ − σo , 26.

where σ and σ o are the bulk conductivities measured, respectively, in the reducing atmosphere and in air. Equation 26 is assumed to be valid because the change in the mobile oxygen-vacancy concentration of CeO2-Gd2O3 is marginal in a reducing atmosphere (15). Figure 10 shows the Arrhenius plots for the electronic component σ e for an atmosphere of Ar + 10% H2 and H2 + 3% H2O. The measured T ∗ was the same as that for σ o, and slopes of the lines gave polaronic activation

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Figure 9 Arrhenius plots for a dense Ce0.9Gd0.1O1.95 ceramic measured in different atmospheres. Inset: Fit of Equations 21–24 to data taken in air [after (11)].

enthalpies Ea ≈ Hp = 0.40 ± 0.01 eV for T > T ∗ and Ea = Hp + Htp ≈ 0.51 ± 0.01 eV for T < T ∗ . Trapping of polarons in the vacancy-ordered clusters at T < T ∗ reflects a stronger coulombic attraction for the polarons in the vacancyordered clusters. Comparison of the activation energies of σ e and σ o shows that the polaronic conduction above T ∗ ≈ 583◦ C is comparable to that for oxideion conduction. In view of the oxidizing atmosphere at the cathode, the effective

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Figure 10 Arrhenius plots for the electronic conductivity σ e of Ce0.9Gd0.1O1.95−δ in two reducing atmospheres [after (11)].

transport number to for oxide-ion conduction across a doped-ceria electrolyte in a SOFC is not prohibitively low. Moreover, a T ∗ < 600◦ C compared with a T ∗ ≈ 800◦ C in yttria-stabilized zirconia makes doped ceria competitive with stabilized zirconia for a SOFC operating below 700◦ C. Also, doped ceria is effectively inert chemically with respect to the electrodes; interdiffusion of lanthanide ions of the ceria with those of a perovskite cathode does not create new phases at the interface that block oxide-ion transport.

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The Sm3+ and Gd3+ ionic radii have the best match to that of the Ce4+ ion, and Sm0.2Ce0.8O2 (SDC) gives the highest oxide-ion conductivity of the rare-earthdoped cerias (16). The open-circuit voltage of an unoptimized hydrogen-air fuel cell with an SDC electrolyte was reduced to about 0.89 V because of the electronic component of the electrolyte conductivity. Nevertheless, despite the lower opencircuit voltage, Lu et al. (17) have obtained a maximum power density of 130 mW/ cm2 at 650◦ C with a single Cu + SDC/SDC/SCF hydrogen-air fuel cell in which SCF = SrCo0.8Fe0.2O3−δ is a mixed oxide-ion/electronic conductor (MIEC) cathode. They have shown that the Cu at the surface of the pores of the porous Cu + SDC anode conducts electrons only between a current collector and the threephase Cu/SDC/dry-H2 interface; reduction of the Ce4+ at the surface of the SDC catalyzes the oxidation of H2. The power density with C4H10 fuel was three times lower, but sputtered Pt on the anode surface can be expected to increase the surfacereaction kinetics for the oxidation of C4H10, and sputtered Pt on the SCF cathode surface has been shown to reduce significantly the cathode overpotential (18). Although Sm-doped ceria is considered to be a promising candidate electrolyte for a SOFC operating at intermediate temperatures, it may be necessary to use it on a bilayer electrolyte where a superior oxide-ion conductor that is stable in an oxygen atmosphere faces the cathode side of the fuel cell.
STABILIZED δ-Bi2O3 High-temperature δ-Bi2O3 has the highest known oxide-ion conductivity, σ o ≈ 2.3 S/cm at 800◦ C; however, it is only stable in the narrow temperature interval between 730◦ C and its melting point at 804◦ C. This phase has a fluorite-related structure with oxide ions randomly occupying three quarters of the tetrahedral interstices of a face-centered-cubic Bi3+-ion sublattice. A neutron diffraction study by Battle et al. (19) has found that nearly half of the O2− ions are displaced from the center of a tetrahedral site toward one of its faces, i.e., toward a potential-energy saddle point between adjacent tetrahedral sites sharing faces with an intervening, empty octahedral site. In a high-temperature X-ray study that takes into account the anharmonic part of the mobile-ion potential, Schulz (20) has shown that the mobile F− ion in the fluorite PbF2 is distributed over the tetrahedral and bottleneck positions with little density in the octahedral sites. From this measurement and the structure of KY3F10, it is apparent that rotation of an elementary F− ion cube from the tetrahedral to the saddle-point positions in the fluorite structure costs little energy (3), which is why stoichiometric PbF2 is an ionic conductor. In δ-Bi2O3, the 6s2 lone pair at a Bi3+ ion is highly polarizable, as is also the case for the Pb2+ ion in PbF2, which lowers further the ionic potential at the saddle-point bottleneck position in δ-Bi2O3. At room temperature, ordering of the oxygen vacancies is found in a monoclinic α-phase (21, 22). On heating through 730◦ C, a first-order α → δ transition is a vacancy order-disorder transition such as that illustrated in Figure 6. The transition enthalpy is 2.7 times the heat of fusion, and the entropy gain is 75% of the total entropy gain on passing from the solid to the liquid state; the transition corresponds to a melting of the anion sublattice (23), which results in an abrupt increase of the total

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Figure 11 Arrhenius plots of total conductivity in air of several oxide-ion electrolytes: 1, Bi0.75Y0.25O1.5; 2, the perovskite La0.9Sr0.1Ga0.8Mg0.2O2.85; 3, Ce0.8Gd0.2O1.9 (12); 4, Zr0.91Y0.09O1.955 (24a); 5, the brownmillerite Ba2In2O5 (37); and 6, δ-Bi2O3 (26).

conductivity σ by three orders of magnitude (24) (see Figure 11). The transition has a large thermal hysteresis; on cooling through 650◦ C, a metastable tetragonal β-phase may also be found at 630◦ C before the stable α-phase is observed, and a second body-centered-cubic γ -phase may also be found at 630◦ C before the stable α-phase is encountered. A large volume change accompanies the transition, and the mechanical properties deteriorate on thermal cycling through the transition. Takahashi et al. (25–27) demonstrated that the δ-phase can be stabilized to lower temperatures by cation substitution for Bi; the stability range can be extended to

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room temperature by incorporation of 22–27 mol% WO3, 25–43 mol% Y2O3, or 35–50 mol% Gd2O3. However, substitution of another cation for Bi lowers the conductivity, and the highest oxide-ion conductivity occurs at the lowest concentration of the substituent required to stabilize the δ-phase to room temperature, which is found for Bi0.8Er0.2O1.5 (28). Figure 11 compares the Arrhenius plot of the conductivity of δ-Bi2O3 with those for Bi0.75Y0.25O1.5 and several other oxideion solid electrolytes. The curve for Bi0.8Er0.2O1.5 is similar, but slightly higher than that shown for Bi0.75Y0.25O1.5. Although the first-order transition between the α and δ phases is suppressed by a rare-earth substitution, a knee at a T ∗ ≈ 873 K, i.e., 600◦ C, reveals a condensation of vacancies into ordered clusters below T ∗ to give an activation energy Ea for oxide-ion conductivity that is described by Equation 23. A σ o ≈ 0.11 and 0.23 S/cm at 650◦ C for Bi0.75Y0.25O1.5 and Bi0.8Er0.2O1.5, respectively, are quite acceptable for an intermediate-temperature fuel cell. However, these stabilized phases have been shown to age at 600◦ C due to transformation to a vacancy-ordered rhombohedral phase having significantly lower oxide-ion conductivity (25, 29–31). Fung et al. (32) have reported that this fatal shortcoming can be suppressed by the addition of less than 5% of ZrO2 or ThO2. Similar small additions of CeO2 have also been shown to suppress aging of Bi0.75Y0.25O1.5 (33). Although Bi2O3-based electrolytes are reduced in the atmosphere at the anode of a SOFC, a thin layer of Sm-based ceria on the anode side of the electrolyte can be expected to alleviate this problem provided the relatively large thermal-expansion coefficient of about 15 × 10−6 K−1 of Bi0.75Y0.25O1.5 (34) does not prohibit it.
PYROCHLORES As in the fluorite structure, the cations of the cubic A2B2O7 pyrochlores form a face-centered-cubic array with oxide ions located in the tetrahedral interstices of the cation array. However, there are two different cations, A and B, that order into alternate (110) rows in every other (001) plane and in alternate ¯ (110) rows in the other (001) planes as is illustrated in Figure 12. This cation ordering gives three distinguishable tetrahedral sites for the anions. In space group Oh7-Fd3m, the 48(f) tetrahedral sites have two A and two B nearest-neighbors, the 8(b) positions have four smaller B nearest-neighbors, and the 8(a) sites have four larger A nearest-neighbors. In the pyrochlore structure, the anion 8(b) positions are vacant, and we may write the formula unit as A2B2O6O , where the O oxygen occupy 8(a) sites and the O oxygen the 48(f) sites. The four B cations that neighbor an oxygen vacancy tend to be electrostatically shielded from one another by displacements x of each 48(f) anion from the center of its tetrahedral interstice toward its two smaller nearest-neighbor B cations. This displacement is to a position where the B cations are in perfect octahedra that share common corners along all the (110) rows of B cations with a B–O–B bond angle α along these rows that is increased from 109◦ 28 to about 132◦ . The 8(a) oxygen atoms remain equidistant from the four nearest-neighbor A atoms, and the A2O subarray is isostructural with anti-SiO2. The fact that the pyrochlore structure is derived from an oxygen-deficient fluorite structure by an ordering of both cations and oxygen vacancies suggests that an

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Figure 12 Cation sublattice for one-quarter unit cell of the pyrochlore structure. Two of the 48(f) anions and one of the 8(b) positions are also shown (34a).

order-disorder transition may lead to a disordered phase exhibiting high oxide-ion conductivity. A key variable that determines the stability of cation ordering is the ratio rA/rB of the ionic radii of the A and B cations. The smaller is rA/rB, the lower is the expected order-disorder transition temperature. Moon & Tuller (35, 36) have reported such a transition in Gd2(Ti1−xZrx)O6O with a primarily oxide-ion conductivity for x > 0.4, but a σ o ≈ 10−2 S/cm at 1000◦ C is not competitive with other oxide-ion electrolytes.

Oxygen-Deficient Perovskites
Removal of the O oxygen from the A2B2O6O pyrochlore structure gives the chemical formula ABO3. If the A and B cations order within a body-centeredcubic cation lattice rather than in a face-centered-cubic cation array, the structure becomes that of perovskite. Bond-length mismatch induces cooperative rotations of the corner-shared BO6/2 octahedral sites; these rotations move the O2−ions from octahedral cation coordination toward saddle-point tetrahedral coordination.

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Moreover, the structure can sustain a large concentration of oxide-ion vacancies. These observations suggest exploration of oxygen-deficient perovskites for oxideion electrolytes. Such an exploration can be extended to oxides containing perovskite layers alternating with other layers such as Bi2O2. Furthermore, where the B sites are occupied by a transition-metal atom, mixed ionic-electron conductors (MIECs) can be obtained for cathode materials. This review concentrates on the oxide-ion electrolytes with perovskite-related structure.
BROWNMILLERITE The ideal ABO3 perovskite structure of Figure 13a consists of a cubic array of corner-shared BO6/2 octahedra with a large A cation at the bodycenter position. A measure of the mismatch of the (A–O) and (B–O) equilibrium bond lengths is the tolerance factor √ t ≡ (A–O)/ 2(B–O). 27.

A t < 1 is accommodated by a cooperative rotation of the octahedra; the most common rotations are about a cubic (001), (111), or (110) axis to give, respectively, tetragonal, rhombohedral, or orthorhombic symmetry. Because the (A–O) bond normally has a larger thermal-expansion coefficient than the (B–O) bond, a dt/dT > 0 as well as the greater vibrational entropy of the more symmetric phases leads to structural changes between distorted phases or between a cooperative rotation and the cubic structure at a transition temperature Tt. In SrTiO3, a tetragonal-cubic transition is found at Tt = 110 K. The oxide ion is stable in either octahedral or tetrahedral cation coordination, and the cooperative oxide-ion displacements toward tetrahedral saddle-point positions between neighboring octahedral B sites occurs with relatively small displacements of the cations. This observation suggested that oxide-ion vacancies in a perovskite may be as mobile as those in an oxygen-deficient fluorite. In order to test this idea, an investigation of the brownmillerite phase of Ba2In2O5 was undertaken (37). The A2B2O5 brownmillerite structure of Figure 13b is derived from the ABO3 perovskite structure by an ordering of the oxygen vacancies into alternate BO2 sheets to give layers of corner-shared BO6/2 octahedra alternating with layers of corner-shared BO4/2 tetrahedra; the tetrahedra and octahedra share corners along the c-axis. This structure is formed where the B cations are stable in both octahedral and tetrahedral symmetry, as is the case for the main group ions Al(III), Ga(III), In(III), and Ge(IV). In this structure, oxide-ion vacancies are introduced without aliovalent substitution on one of the cation subarrays, which eliminates a variation of the oxide-ion potential in the structure. Ba2In2O5 was chosen for investigation because of the large size of the cations, which offered the greatest free volume for oxygen diffusion. The Arrhenius plot for σ o(T) of Ba2In2O5 is shown in Figure 11; the measurement was made under an oxygen partial pressure pO2 ≈ 10−6 atm. A sharp discontinuity at Tt ≈ 930◦ C marks a first-order order-disorder transition, and the change in slope near 650◦ C is due to a temperature-dependent enthalpy Hg in Equation 17 to excite an oxide ion to an interstitial site (see Figure 6). Although

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Figure 13 The structure of (a) cubic perovskite and (b) brownmillerite.

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long-range vacancy ordering is destroyed at the orthorhombic-cubic transition at Tt (38), considerable short-range order persists above Tt. Prasanna & Navrotsky (39) have shown with step-scanning calorimetry that the entropy change at Tt is only 4% of that calculated for a total order-disorder transition. Although the temperature range of the conductivity measurements above Tt was too small to achieve complete disorder, nevertheless the data reveal an activation energy that approaches a Hm comparable to that found in oxides with the fluorite structure.
OXYGEN-DEFICIENT PEROVSKITES In an attempt to stabilize the disordered-vacancy phase to lower temperatures, Ba3In2MO8 compounds with M = Zr, Ce, or Hf were studied (37). As in the case of Bi0.75Y0.25O1.5, the introduction of disordered In(III) and M(IV) ions on the B sites lowered σ o and replaced the first-order order-disorder transition at 930◦ C with a change of slope of log σ o versus 1/T at a T ∗ ≈ 800◦ C characteristic of the formation of vacancy-ordered clusters below T ∗ . A subsequent study (40) of the system BaZr1−xInxO3−0.5x revealed that water is reversibly inserted/extracted from the oxygen vacancies in order to stabilize Ba2+ in 12-fold oxygen coordination and Zr(IV) in 6-fold oxygen coordination; these large, basic cations take the oxygen of water or CO2 to complete their stable oxygen coordination, which makes it necessary to replace Ba2+ with La3+ and Zr(IV) with a cation that is stable in 4-fold oxygen coordination. Even orthorhombic Ba2In2O5 takes water from the atmosphere to become cubic Ba2In2O5 · H2O at room temperature, which makes it a good proton conductor below 400◦ C. However, problems with water insertion and the long-range first-order order-disorder transition are overcome in Ba0.6La0.4InO2.7, which has an oxide-ion conductivity similar to that of yttria-stabilized zirconia (Figure 14) (41). However, the best perovskite oxide-ion electrolyte is a Sr- and Mg-doped LaGaO3 (42, 43). The Arrhenius plot of σ o for this electrolyte is shown in both Figure 11 and Figure 14. The oxygen-deficient, cubic perovskite La0.9Sr0.1Ga0.8Mg0.2O2.85 was shown to have an oxide-ion conductivity σ o > 10−2 S/cm at 600◦ C with a transport number to ≡ σ o/σ ≈ 1 over the oxygen partial-pressure range 10−20 < pO2 < 0.4 atm (42). Substitution of 10% of the La by Nd was found to suppress p-type electronic conduction at highest oxygen partial pressures (44). The perovskite does not absorb water and showed no sign of aging over 140 h of operation at 750◦ C; its thermal expansion coefficient α ≈ 10−5 K−1 is similar to that of yttria-stabilized zirconia (42). The σ o versus T−1 plot deviates from an Arrhenius behavior, exhibiting a knee at a T ∗ ≈ 600◦ C that is characteristic of a condensation of ordered-vacancy clusters below T ∗ in accordance with Equations 21–24. Another advantage of this electrolyte is that a high sample density can be readily achieved. However, the singlephase, cubic-perovskite region of the LaO1.5−SrO−GaO1.5−MgO phase diagram is limited. A careful study of the bulk oxide-ion conductivity contours at 800◦ C and 702◦ C for La1−xSrxGa1−yMgyO3−0.5(x+y) (Figure 15) (45), has pinpointed the optimum values of x and y as La0.8Sr0.2Ga0.83Mg0.17O2.815. This composition is designated LSGM in what follows.

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Figure 14 Conductivity σ o(T ) of La0.9Sr0.1Ga0.8Mg0.2O2.85, La0.4Ba0.6InO2.7, and (ZrO2)0.9(Y2O3)0.1 [after (41)].

The bulk conductivity of LSGM is almost independent of oxygen partial pressure from 10−20 ≤ pO2 ≤ 1 atm, which indicates pure oxide-ion conductivity with negligible electronic conduction. Two deleterious impurity phases were identified, LaSrGaO4 and LaSrGa3O7. Electron microscopy and ac-impedance spectroscopy have shown that LaSrGa3O7 does not conduct oxide ions and forms a blocking phase at the grain boundaries in the samples La0.8Sr0.2Ga1−yMgyO3−.05(0.2+y) for 0.05 ≤ y ≤ 0.10. In contrast, the impurity LaSrGaO4, which was found for x = 0.20 and 0.25 ≤ y ≤ 0.30, gives no grain-boundary contribution to the impedance (46).

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Figure 15 Contours of oxide-ion conductivity of La1−xSrxGa1−yMgyO3−0.5(x+y) at (a) 800◦ C and (b) 702◦ C [after (46)].

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It was assumed that the liquid state of LaSrGaO4 during sintering improves the grain-boundary contact to suppress the grain-boundary contribution to the oxideion resistivity. In order to use LSGM as the solid oxide-ion electrolyte of a SOFC, it is necessary to examine not only the mechanical, but also the chemical compatibility of the electrolyte and the electrodes. If a composite NiO + LSGM is used as the anode, the NiO is reduced to elemental Ni by the fuel. This anode design is used for a hydrogen-air fuel cell because nickel is an excellent catalyst for the hydrogen-oxidation reaction. However, NiO reacts with LSGM at the fabrication temperature to form LaNiO3 at the anode-LSGM interface, and metallic LaNiO3 does not conduct O2− ions (47). An initial attempt to alleviate this problem involved deposition of a thin layer of Sm0.2Ce0.8O1.9 (SDC) on the anode side of the electrolyte with a NiO + SDC anode. However, chemical reactions at elevated temperatures between the LSGM, CeO2, and NiO have shown that La3+ is a fairly mobile species in the LSGM electrolyte. La diffusion driven by the gradient of activity can alter the composition of the LSGM, leading to the formation of phases at the ceria-LSGM interface that block oxide-ion transport; either LaSrGa3O7 or LaSrGaO4 is formed at the interface depending on whether La diffuses out of or into the LSGM, respectively. As a result, the SDC layer and the NiO + SDC composite anode show sensitivity to the preparation conditions. A lower anode overpotential was obtained with La0.4Ce0.6O1.8 (LCD) in place of SDC; the LDC composition was chosen in order to achieve an iso-La chemical activity across the interface (48). The NiO does not react with the LDC to form LaNiO3. The LSGM is chemically stable with hydrocarbon fuels; it is not necessary to deposit an LDC layer on the anode side of an LSGM electrolyte if CuO replaces NiO to avoid carbon formation as the anode with hydrocarbon fuels. Energy-dispersive-spectrometry line scans and ac-impedance spectroscopy were used to investigate the chemical reactions between LSGM and two metallicperovskite cathode materials, La0.84Sr0.16MnO3 (LSM) and La0.5Sr0.5CoO3−δ (LSC); the latter is a mixed oxide-ion/electronic conductor (MIEC) in the oxidizing atmosphere at the cathode, the former does not conduct oxide ions and therefore must be deposited as a porous layer so as to allow gaseous O2 to reach the O2 + LSM + LSGM three-phase interface. Significant interdiffusion of Co into LSGM and Ga into LSC was found at the LSC/LSGM interface even at relatively low fabrication temperatures. In contrast, only a small interdiffusion of Mn into LSGM and Ga into LSM was detected at the LSM/LSGM interface (49). However, the B cation interdiffusion at the cathode/electrolyte interface does not appear to cause any serious problem. Monitoring cathode overpotentials of LSGM-based SOFCs identified SrCo0.8Fe0.2O3−δ (SCF) as the best mixed oxide-ion/electronic cathode material (50), and earlier studies (51, 52) had shown that SCF has the highest oxygen permeation flux among the known mixed oxide-ion/electronic conductors in an oxidizing atmosphere. A later study of oxygen permeation through SCF and La1−xSrxCoO3−δ showed that the kinetics of the surface reactions, chemisorption of O2 on one side and desorption of O2 on the other side, and not the bulk oxygen

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Figure 16 Cell voltage and power density as a function of current density at 600, 700, and 800◦ C for a Pt:SCF/LSGM/LDC/LDC + Ni SOFC with dry H2 as fuel. The LSGM thickness is 200 µm [after (18)].

diffusion were the rate-limiting steps (53). Verification of this deduction was obtained by a 40% reduction of the cathode overpotential of an SCF/LSGM/LDC/LDC + Ni SOFC with Pt sputtered on the surface of the SCF cathode layer (18). With a 200-µm-thick LSGM electrolyte, a maximum power output of 1400 mW/cm2 was obtained at 800◦ C with dry H2 as fuel and air as oxidant (Figure 16). This performance compares favorably with hydrogen-air fuel cells having a thin (10– 20 µm) yttria-stabilized zirconia layer as the electrolyte.

BIMEVOX
Aurivillius phases have an intergrowth of (Bi2O2)2+ sheets and perovskite blocks (An−1BnO3n+1)2− that contain n layers of octahedral B sites. The (Bi2O2)2+ layer consists of a planar square array of oxygen atoms with Bi3+ ions above and below alternate squares, each situated above an A site position of the adjoining perovskite layer. Below 604◦ C, the oxidation catalyst Bi2MoO6 has a tetragonal γ phase with the Aurivillius n = 1 structure illustrated in Figure 17 (54). Bi2VO5.5 has an oxygen-deficient Aurivillius n = 1 structure; it was discovered independently by Bush & Venetsev (55) and by Debreuille-Gresse (56). On heating, Bi2VO5.5

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Figure 17 The ideal structure of Bi2MoO6.

undergoes two transitions, from a monoclinic α to an orthorhombic β phase at 450◦ C, and from the β phase to a tetragonal γ phase at 570◦ C. Abraham et al. (57) found a high oxide-ion conductivity in the tetragonal γ phase; they subsequently stabilized the tetragonal, vacancy-disordered phase to room temperature by substituting other elements for vanadium (58). These stabilized oxide-ion conductors were identified as BIMEVOX, where ME represents the substituted metal atom. Highest oxide-ion conductivities were obtained with BICUVOX-10, Bi2V0.9Cu0.1O5.35. This composition contains the lowest concentration of copper

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Figure 18 Arrhenius plots of oxide-ion conductivity in air for several compositions Bi4V2−xCuxO11−δ [after (59)].

at which the room-temperature structure is tetragonal (59). Arrhenius plots of σ o(T) versus copper concentration x for BICUVOX are shown in Figure 18. Yan & Greenblatt (60) have obtained similar excellent lower-temperature oxide-ion conductivity with γ -Bi2V0.85Ti0.15O5.425 (σ o = 4 · 10−4 S/cm at 227◦ C). Vannier et al. (61) have shown that the in-plane σo⊥ is about two orders of magnitude higher than the c-axis σ o||. At temperatures higher than about 500◦ C, BICUVOX begins to be reduced at oxygen partial pressures pO2 < 10−2 atm, which introduces n-type electronic conduction; and in the reducing atmosphere at the anode of a SOFC, an irreversible reduction to other phases takes place. However, in air BICUVOX has a transport number to ≈ 1 and has been shown to separate oxygen from air at

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437◦ C with 100% efficiency (62). Although practical use of BIMEVOX ceramics for electrochemical applications is complicated by a high-chemical reactivity, low-mechanical strength, and a high-thermal-expansion coefficient, Yaremchenko et al. (63) have found mechanical and chemical compatibility of BICUVOX with a La0.7Sr0.3CoO3−δ electrode in an oxidizing atmosphere. For use in a SOFC, it will be necessary to find a mixed oxide-ion/electronic conductor such as SDC that is mechanically compatible for deposition on the anode side of the electrolyte.

Concluding Remarks
This brief review highlights the fact that the oxide-ion electrolyte of choice for the SOFC is not yet clarified. The need to replace ceramic interconnects with alloys, as well as the cost of manufacture and maintenance of a fuel-cell stack, makes it mandatory to operate below 800◦ C, but these temperatures are at the technical limit that can be achieved with yttria-stabilized zirconia as the electrolyte; they require fabrication of dense ceramic membranes of large area that are only 10 to 20 µm thick. This fact continues to motivate the search for improved materials. The high oxide-ion conductivities found at lower temperatures

Figure 19 Comparison of the oxide-ion conductivity of La1.61GeO5−δ and La1.5Sr0.17GeO5−δ with those of three conventional oxide-ion electrolytes [after (64)].

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Figure 20 Arrhenius plot of the oxide-ion conductivity of La2Mo2O9 and La2Mo2−xWxO9 [after (66)].

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in Bi0.75Y0.25O1.5 and BIMEVOX demonstrate that the necessary oxide-ion conductivities for intermediate-temperature (500–700◦ C) operation exist, but these materials are not stable in the reducing atmosphere at the anode of a SOFC. It remains to be seen whether a surface layer on the anode side of these electrolytes can make these electrolytes viable. On the other hand, the lanthanide-doped cerias and LSGM promise to allow operation at 650◦ C provided they are used together either to block the electronic component in the doped ceria with the LSGM, or with the ceria, to block unwanted anode/electrolyte chemical reactions and/or to provide a catalytic surface for fuel oxidation at the anode. Meanwhile, the search for alternative oxide-ion electrolytes continues. For example, the monoclinic structure of La2GeO5 is retained on removal of La over the compositional range 0 ≤ x ≤ 0.45 in La2−xGeO5−δ. The parent structure consists of isolated (GeO4)4− units separated by an (La2O)4+ matrix connected in three-dimensions. Lanthanum-deficient compositions have been found to exhibit a competitive oxide-ion conductivity in air above 700◦ C, but vacancy ordering lowers σ o below 700◦ C (64). Although stabilization of the high-temperature phase to lower temperatures by the introduction of Sr in La1.5Sr0.17GeO4.37 lowers σ o at high temperatures, the oxide-ion conductivity remains higher than that of yttriastabilized zirconia (see Figure 19). Lacorre et al. (65) have reported on oxide-ion conductivity in La2Mo2O9 that is superior to that of stabilized zirconia above a first-order transition at 580◦ C. This structure consists of isolated (MoO4)2− units in a three-dimensional matrix of (La2O)4+. The authors make an interesting comparison with β-Sn2WO4 in which the 5s2 lone pairs on the Sn2+ ions are projected into two anion vacancies per formula unit to electrostatically screen the Sn2+ ions from one another. In the (La2O)4+ matrix of La2Mo2O9, one of the two vacancies is occupied by an O2− ion in an ordered manner in the low-temperature α phase, but the O2− ions of the matrix become disordered over the two sites in the high-temperature β phase. The first-order α-β order-disorder transition is of the type described in Figure 6. In this system, substitution for La or Mo also stabilizes the high-temperature phase, but at the expense of lowering σ o above 500◦ C, as is illustrated in Figure 20 for La2Mo2−xWxO9 (66). Compounds with La2Mo2O9 as parent are now referred to as members of the LAMOX family of oxide-ion electrolytes. The stability of the (MoO4)2− or (WO4)2− polyanions in a reducing atmosphere has not been reported. Nevertheless, this family suggests that partial replacement of lone pairs by oxide ions in a three-dimensionally connected matrix may lead to the discovery of other oxide-ion electrolytes. ACKNOWLEDGMENTS The Robert A. Welch foundation of Houston, Texas and the ARL Collaborative Technology Alliance in Power and Energy, Cooperative Agreement No. DAAD1901-2-0010 are thanked for financial support.

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