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Journal of Alloys and Compounds 494 (2010) 190195

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Journal of Alloys and Compounds


journal homepage: www.elsevier.com/locate/jallcom

Review

Oxygen transport in perovskite and related oxides: A brief review


A. Chroneos a, , R.V. Vovk b , I.L. Goulatis b , L.I. Goulatis c
a

Department of Materials, Imperial College London, London SW7 2AZ, United Kingdom Kharkov National University, 4 Svoboda Sq., 61077 Kharkov, Ukraine c Department of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechniou str., Zografou 157 80, Greece
b

a r t i c l e

i n f o

a b s t r a c t
Perovskites and related oxides are a very important class of functional materials that exhibit a range of stoichiometries and crystal structures. The oxygen diffusion mechanisms and activation energies in these materials are highly inuenced by the composition, stoichiometry and crystal structure. We review the signicance of a range perovskite related oxides but focus on two characteristic materials: La2 NiO4+ and LnBa2 Cu3 O7 (where Ln = rare-earth cations). La2 NiO4+ is considered as a cathode material for solidoxide fuel cells, whereas LnBa2 Cu3 O7 is the archetypal superconducting oxides. 2010 Elsevier B.V. All rights reserved.

Article history: Received 27 September 2009 Received in revised form 12 January 2010 Accepted 16 January 2010 Available online 25 January 2010 PACS: 66.30.Lw 82.47.Ed 61.43.Bn Keywords: Perovskite oxides Oxygen diffusion Anisotropy

Contents 1. 2. 3. 4. 5. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . RuddlesdenPopper series of layered oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . LnBa2 Cu3 O7 superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other materials of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190 191 193 193 194 194 194

1. Introduction Perovskite and related oxides have been extensively studied for a range of applications including solid-oxide fuel cell (SOFC) electrodes and high temperature superconductors [17]. Fig. 1 represents the archetypal ABO3 crystal structure that is cubic [8]. The perovskite structure is common in many ternary oxides in which the A and B cations have signicantly different sizes. The larger cations, A, and the oxygens form a face-centered cubic (FCC) lattice [8]. The smaller cations, B, occupy octahedral sites in this FCC lattice and are only surrounded by oxygen nearest neighbors. These B cation occupied octahedra share corners with each other, but share

Corresponding author. E-mail address: alexander.chroneos@imperial.ac.uk (A. Chroneos). 0925-8388/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2010.01.071

faces with the dodecahedra surrounding the A cations [8]. The A and B cations are shielded from one another by the oxygen ions [8]. The defect chemistry of perovskite materials can be controlled to an extent by doping. Introducing a lower valence cation to substitute for an A-site results in the formation of oxygen vacancies and a hypostoichiometric perovskite [9]. However, there are exceptions such as La1x Srx MnO3 for which the Sr substitution of La can lead to oxygen excess under oxidizing conditions and the formation of cation vacancies. If the A-site cations are substituted with cations of higher valence then A-site vacancies form. The substitution of the B-site can lead to both hypostoichiometric and hyperstoichiometric perovskites. The formation of oxygen vacancies or interstitials by doping is important as these facilitate oxygen via the vacancy, interstitial or interstitialcy mechanisms. The aim of the present contribution is to briey review oxygen transport in model perovskite and perovskite related systems

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Fig. 1. The cubic perovskite structure.

focusing on recent advances. The emphasis is on the diffusion mechanism of La2 NiO4+ , a material for which a number of conicting experimental works exist in the literature, and LnBa2 Cu3 O7 compounds that are important high temperature superconductors. This review is not a comprehensive literature survey and the references are selected to guide the readers towards systems of possible academic and technological interest. Readers are also referred to relevant comprehensive reviews of related materials [4,915]. 2. RuddlesdenPopper series of layered oxides Presently a number of oxides are being considered for SOFC cathode applications with the materials design rules requiring improved performance at lower temperatures and resistance to degradation during operation. An important class of candidate materials for the next generation of SOFC cathodes is the perovskite related RuddlesdenPopper (RP) series of layered oxides (formula An+1 Bn O3n+1 ). This is due to their electrochemical, catalytic and electrical properties as well as their thermal and mechanical stability. The rst members of the RP series (for n = 1, A2 BO4 ) such as La2 NiO4 are being considered for oxygen sensors, oxygen separation membranes and as cathodes for intermediate temperature SOFC (ITSOFC) [1627]. La2 NiO4 has the K2 NiF4 structure which has been investigated in great detail ever since the observation of high-temperature superconductivity in La2x Bax CuO4 by Bednorz and Mller [28]. Skinner [20] determined with the use of in situ high temperature neutron powder diffraction that in the temperature range 4231073 K La2 NiO4 exhibits the tetragonal symmetry (space group I4/mmm). At room temperature La2 NiO4 forms in the orthorhombic symmetry (space group Cmca) [29]. The structural polymorphs of La2 NiO4 are dependent upon the temperature and changes in stoichiometry. These materials can exhibit both an oxygen deciency (hypostoichiometry, La2 NiO4 ) and an oxygen excess (hyperstoichiometry, La2 NiO4+ ). These are accommodated by the formation of oxygen vacancies (represented by VO in Krger-Vink notation) and oxygen interstitials (represented by Oi in Krger-Vink notation) respectively. Consequently, in these materials oxygen diffusion can be mediated by either oxygen vacancies or oxygen interstitials depending upon the oxygen stoichiometry. The oxygen diffusion coefcient DO can be dened as DO = DV [VO ] + Di [Oi ]

(1)

where DV and Di are the vacancy and interstitial diffusion coef cients, whereas [VO ] and [Oi ] represent the oxygen vacancy and interstitial concentrations respectively. For hypostoichiometric La2x Srx CuO4 Opila et al. [30] determined that there is signicant anisotropy between the oxy-

gen diffusion in the ab plane and the c-axis. In tetragonal La1.85 Sr0.15 CuO4 Savvin et al. [31], using molecular dynamics (MD), predicted oxygen diffusivities that were higher by several orders of magnitude compared to the radioactive tracer study of Routbort et al. [32] on dense polycrystalline samples. Interestingly, however, for La1.85 Sr0.15 CuO4 the predicted activation energy of diffusion of Savvin et al. [31], 0.86 eV is in excellent agreement with the determined value of Routbort et al. [32] 0.84 eV. La2 NiO4 is characterized by an oxygen hyperstoichiometry that inuences oxygen diffusion [18]. Previous thermogravimetric analyses of La2 NiO4+ [3335] have revealed a range of oxygen hyperstoichiometries that are dependent upon the experimental conditions (for example the thermal history of the samples). Considering, the diffusion mechanism and activation energy, in previous experimental work the mechanism of diffusion is not well dened whereas there is a wide range of determined activation energies, from 0.19 eV to 0.90 eV (see Table 1) [17,21,36]. Additionally, in Table 2 we compare the oxygen diffusion and overall conductivity of La2 NiO4+ with other SOFC cathode materials [12,34,3743]. These results highlight the potential applicability of La2 NiO4+ as a cathode material. To illuminate these differences a closer look on the crystallography and hyperstoichiometry of La2 NiO4+ is required. La2 NiO4 is effectively constructed from alternating NiO2 and (LaO)2 layers, which have different ideal translations and consequently have to be adjusted to form a crystal with a uniform lattice spacing [44]. A way to relax the stressed (LaO)2 layers is the introduction of oxygen interstitials [44]. This is supported by the neutron diffraction studies of Wegner and OKeeffe [45], which veried that excess oxygen in La2 NiO4+ can be accommodated as oxygen interstitials in the (LaO)2 layers. The accommodation and transport of oxygen interstitials in La2 NiO4+ was studied in detail in previous static atomistic simulation studies [18,25,46]. In La2 NiO4+ the oxygen interstitial is located in the (LaO)2 layers and is surrounded by La cations (Fig. 2). These La cations form a tetrahedron around the oxygen interstitial [47]. The methodology and efcacy of static atomistic simulation techniques based on the pair potentials to describe perovskite related materials and other oxides have been discussed in previous work [25,4853]. Bassat et al. [21] determined that oxygen excess in La2 NiO4+ leads to greater oxygen diffusion. Frayret et al. [23] using density functional theory (DFT) in conjunction with Bader analysis [54] predicted that the oxygen interstitial in La2 NiO4+ is doubly negatively charged (O2 ). As it is implied by Eq. (1) vacancy mediated diffusion requires the formation of oxygen vacancies. Oxygen interstitials will practically dominate in La2 NiO4+ over the temperature range of the operation of SOFC. The supersaturation of oxygen interstitials will reduce the concentration of oxygen vacancies, through the oxygen Frenkel reaction equilibrium, leading effectively to the demise

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Table 1 Activation energies of oxygen self-diffusion in La2 NiO4+ . Methodology Experimental Experimental Experimental Static atomistic simulation Molecular dynamics
a

Ea (eV) 0.19 0.54 0.88 0.55a 0.51

Temperature range ( C) 340600 350700 460900 427727

Comment Epitaxial thin lm Polycrystal, TOF-SIMS Single crystal, ab plane Vacancy mechanism Interstitialcy mechanism

References [36] [35] [21] [25] [55]

Activation energy of migration.

Table 2 Oxygen self-diffusion coefcient (D* ) at T = 773 K, activation energy of diffusion (Ea ) and overall conductivity at T = 7731023 K data for La2 NiO4+ and other important cathode materials. Compound La2 NiO4+ Ba0.5 Sr0.5 Co0.8 Fe0.2 O3 GdBaCo2 O5+ La0.5 Sr0.5 CoO3 La0.8 Sr0.2 MnO3 D* (cm2 /s) 3.3 109 1.2 107 2.8 1010 1.5 1010 4.5 1020 Ea (eV) 0.56 0.50 0.60 1.41 2.80 (S/cm) 5565 1055 550925 13001800 120130 References [34,35] [41,43] [37,42] [12,38,40] [12,38,39]

of the vacancy mechanisms. Nevertheless, in what follows we will review for completeness also studies, which investigated the energetics of vacancy diffusion mechanisms. Cleave et al. [25] used a static simulation approach to investigate vacancy and interstitial migration pathways in stoichiometric tetragonal La2 NiO4 . According to this study the most energetically favorable mechanism for oxygen migration is the vacancy mechanism in the ab plane with a migration energy barrier of 0.55 eV [25]. Recent MD work [55] predicts that in stoichiometric La2 NiO4 the oxygen diffusivities are insignicant even at high temperatures. Additionally, cation migration is predicted by MD to be insignicant in agreement with previous studies in perovskite-type oxides,

Fig. 2. (a) MD prediction of the oxygen ion density in the (0 1 0) plane of La2 NiO4.09 and the isosurface connecting the oxygen diffusion sites at T = 900 K ([55]Reproduced by permission of the Royal Society of Chemistry). (b) The two-dimensional network of oxygen diffusion paths in (Pr0.9 La0.1 )2 (Ni0.74 Cu0.21 Ga0.05 )O4+ that was revealed using the maximum entropy method nuclear density analysis from neutron diffraction data (reprinted with permission from [27]. Copyright 2008 American Chemical Society). (ce) Characteristic snapshots of the interstitialcy diffusion sequence during MD simulations of La2 NiO4.09 at T = 900 K. Interstitial oxygen ions and vacancies are represented by yellow spheres and squares respectively ([55]Reproduced by permission of the Royal Society of Chemistry).

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which determined that cation diffusion coefcients are orders of magnitude lower than oxygen diffusion coefcients [56]. Cleave et al. [25] also considered the interstitial migration mechanism for oxygen interstitials, O2 , and predicted the activation energy of migration to be 0.86 eV. Frayret et al. [23] predicted, using DFT, a migration energy barrier for the oxygen interstitial mechanism of 1.2 eV. The difference in the predicted activation energies of oxygen migration between the two computational approaches can be traced on the assumptions in both, the small cell used in the DFT study and the direct path between the two interstitial sites in the study of Frayret et al. [23]. Direct experimental evidence for oxygen interstitial transport in the ab plane of related tetragonal La2 NiO4+ is scarce. Yashima et al. [27] employed neutron scattering experiments and analysis based on the maximum entropy method to demonstrate that oxygen atoms move via an interstitial process in the ab plane of tetragonal (Pr0.9 La0.1 )2 (Ni0.74 Cu0.21 Ga0.05 )O4+ (see Fig. 2(b)). The recent experimental work of Sayers et al. [35] revealed an activation energy of oxygen migration of 0.54 eV in La2 NiO4+ . This is consistent with the most recent MD work [55] that supports an O2 interstitialcy mechanism in the ab plane with migration activation energy of 0.51 eV. In the predicted interstitialcy mechanism the oxygen interstitial displaces an apical oxygen ion from the NiO6 octahedron, which in turn progresses to an adjacent oxygen interstitial site (see Fig. 2). This mechanism is predicted for a range of oxygen hyperstoichiometries (0.055 0.12) and temperatures (8001100 K). As mentioned previously Cleave et al. [25] predicted an oxygen migration energy of 0.55 eV for the vacancy mechanism, however, the activation energy of diffusion will have to account for the formation energy of oxygen vacancies, which is high for hyperstoichiometric La2 NiO4+ . The dominant oxygen interstitialcy mechanism predicted by the MD work [55] was not considered in the static simulation study of Cleave et al. [25]. Finally, it is of interest that the MD simulations observe a strongly anisotropic thermal ellipsoid for the O1 site in excellent agreement with the study of Skinner [20].

3. LnBa2 Cu3 O7 superconductors Bednorz and Mller [28] investigations on superconducting materials resulted in La2x Bax CuO4 with a critical temperature of 40 K. Soon after this groundbreaking work, YBa2 Cu3 O7 with a critical temperature of 93 K was discovered [8]. YBa2 Cu3 O7x and its rare-earth analogues have been and are extensively investigated [5759,2,60,61,5,6267]. YBa2 Cu3 O7 and related cuprate superconductors can be effectively viewed as a combination of rocksalt and perovskite units [68]. In Fig. 3 the crystal structure of YBa2 Cu3 O7 is represented with the two characteristic non-equivalent Cu sites. These are the fourfold coordinated Cu sites from the CuO chains and the vefold coordination sites that form layers of square pyramids, which contact at their corners. In YBa2 Cu3 O7 the oxygen stoichiometry is dependent upon the temperature of annealing and the pressure. Interestingly, oxygen vacancies order along [68]. Yttrium can be substituted with most rare-earth elements with small effect on the superconducting properties. Diffusion is a very important physical phenomenon that can inuence the processing of materials. The study of oxygen diffusion in LnBa2 Cu3 O7 has been motivated by the need to control the oxygenation of these compounds. Oxygenation can be a signicant problem as it affects the transition temperature and other properties of LnBa2 Cu3 O7 compounds [69]. There have been a numerous experimental diffusion studies of LnBa2 Cu3 O7 compounds [6978]. As highlighted in the previous section MD simulations can identify the oxygen transport mechanisms and
Fig. 3. The YBa2 Cu3 O7 crystal structure. Cu is four-coordinated in CuO chains and ve-coordinated in Cu sheets.

the energetics of oxygen diffusion. There have been a number simulation studies on LnBa2 Cu3 O7 [7983] and other cuprate superconductors, for example HgBa2 Ca2 Cu3 O8+ [84]. In Table 3 the activation energies and pre-exponential factors as well as the ionic radii of the rare-earth atoms and Y are presented. Based on these results it can be concluded that there is an increase in the activation energy and the pre-exponential factor of oxygen diffusion with an increase in the ionic radius of Ln (see Table 3). Additionally, the MD work of Zhang and Catlow [82] conrms the determined activation energy of YBa2 Cu3 O7 but underestimates the pre-exponential factor (see Table 2). 4. Other materials of interest Aluminate perovskites, LnAlO3 , have been investigated for decades due to their advantages that include their stability to reduction and volatilization, low cost, and moderate thermal expansion [8587]. However, their low oxygen ionic conduction is a signicant disadvantage [4]. Commonly with other perovskite oxides the oxygen ion conductivity in LnAlO3 decreases with decreasing A-site radius [4]. Doping LaAlO3 with Sr cations increases the oxygen hypostoichiometry and importantly the conductivity. La0.9 Sr0.1 Al1x Mgx O3 that is doped with less than 10% of Mg on the B-sublattice is one of the most promising aluminate

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Table 3 Experimental [69] and MD [82] and activation energies, pre-exponential factor and ionic radii for LnBa2 Cu3 O7x compounds. Methodology Experimental Experimental Experimental Molecular dynamics Compound ErBa2 Cu3 O7 DyBa2 Cu3 O7 YBa2 Cu3 O7 YBa2 Cu3 O6.91 Ionic radius () 0.88 0.91 0.93 0.93 Ea (eV) 0.760.834 0.93 0.975 0.98 DO (cm2 /s) 0.002710.031 0.038 0.057 0.000141

perovskites [4,86,88]. Additional, gains in the ionic conductivity can be achieved by the doping with gallium, however, this leads to the increase of cost [87]. A systematic MD study would be able to tailor the properties of these materials by exploring a wide compositional range and a range of dopants. Gallate perovskites such as LaGaO3 , are promising materials for intermediate temperature (7701100 K) electrochemical cells [4,8992]. Doping with Mg cations on the Ga-sublattice increases the oxygen vacancy concentration [4]. Additionally, the introduction of Sr in the La-sublattice leads to a less pronounced lattice distortion compared to the incorporation of Ca or Ba and is benecial for the ionic conductivity [9395]. For these perovskite materials, La1x Srx Ga1y Mgy O3 , the maximum ionic transport is accomplished when x is in the range 0.10.2 and y in the range 0.150.2 [4]. Recent work by Taskin et al. [96,97] proposed the introduction of double perovskites, AAB2 O5 , in cathode applications for SOFC. Tarancon et al. [98] used secondary ion mass spectrometry to study oxygen self-diffusion in GdBaCo2 O5+ . They determined high oxygen diffusivity and an activation energy for the tracer diffusion coefcient of 0.6 eV. Clearly it is of interest to study analogues of GdBaCo2 O5+ with other cations in the A-site. For example, Kim et al. [99,100] recently determined that oxygen diffusion is faster in PrBaCo2 O5+ . Interestingly, oxygen diffusion in Sr0.75 Y0.25 CoO2.625 is isotropic [101]. The key in the presented isotropy of Sr0.75 Y0.25 CoO2.625 is the partially occupied O4 sites that effectively function as a source of vacancies [101]. This is because the O2 atoms move into the partially occupied O4 sites creating vacancies at O2 sites. In turn these vacancies move to the CoO1/O2 octahedra (ab plane migration) but also along the O2O1O2 pathway (c-axis migration) [101]. 5. Summary The most recent MD and experimental studies conrm the highly anisotropic nature of oxygen diffusion in tetragonal La2 NiO4+ . The MD work supports an O2 interstitialcy mechanism in the ab plane with migration activation energy of 0.51 eV in excellent agreement with the work of Sayers et al. [35] that predicted an activation energy of 0.54 eV. Oxygen diffusion in LnBa2 Cu3 O7 compounds is dominated by vacancies with both the experimental and MD results being consistent for YBa2 Cu3 O7 . It has been appreciated that molecular dynamics simulations based on simple interatomic potential models can provide a signicant insight into the mechanism and energetics of oxygen self-diffusion of very complex oxide materials. Given the great number of compositions that are currently being considered these computational techniques can effectively support experiment by guiding the studies to the more promising materials and providing detailed information that are not easily accessible otherwise. It would be interesting to incorporate charge-transfer phenomena in the interatomic potential models to investigate possible compensation mechanisms that could inuence the oxygen diffusion. In that respect DFT can also complement in the understanding of diffusion mechanisms and processes in inorganic materials as have previous successful predictions demonstrated [23,102107].

Acknowledgements The authors thank John Kilner, David Partt, and Robin Grimes of Imperial College London for useful discussions. References
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