Crystal chemistry and optimization of conductivity in 2A, 2M and 2H alkaline earth lanthanum germanate oxyapatite electrolyte polymorphs

Calcium (La sub(10-x)Ca sub(x)Ge sub(6)O sub(27-x)/2 0

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Veröffentlicht in:Solid state ionics 2010-08, Vol.181 (25-26), p.1189-1196
Hauptverfasser: Pramana, Stevin S., Baikie, Tom, Kendrick, Emma, Schreyer, Martin K., Slater, Peter R., White, T.J.
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container_end_page 1196
container_issue 25-26
container_start_page 1189
container_title Solid state ionics
container_volume 181
creator Pramana, Stevin S.
Baikie, Tom
Kendrick, Emma
Schreyer, Martin K.
Slater, Peter R.
White, T.J.
description Calcium (La sub(10-x)Ca sub(x)Ge sub(6)O sub(27-x)/2 0
doi_str_mv 10.1016/j.ssi.2010.06.044
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The lattice parameters obtained from Rietveld refinement of powder X-ray diffraction data showed that pseudomorphic transformations from 2A to 2H occurred as the alkaline earth was introduced. The likely appearance of an intervening 2M pseudomorph was not confirmed directly in this study; however, compositionally dependent inflections in cell constants and abrupt changes in oxygen mobility as a function of temperature support its existence, particularly for low alkaline earth contents. Oxygen excess apatites La sub(9)AEGe sub(6)O sub(26.5) (AE = Ca, Sr, Ba) prove most promising as solid oxide fuel cell (SOFC) electrolytes at intermediate temperatures, by delivering the optimal compromise between higher mobile oxygen concentration and lowering of activation energy. In contrast, stoichiometric La sub(8)AE sub(2)Ge sub(6)O sub(26) showed inferior conductivity, because although the activation energy was reduced, the proportion of extrastoichiometric oxygen was negligible. Atomistic modeling suggests that interstitial oxygen is located near (0, 1/2, 1/2) and causes the O3 position to be split statistically into the (0.050, 0.278, 0.587) and (0.084, 0.335, 0.565) sites. These co-existing locations may facilitate inter-tunnel oxygen transport.</description><identifier>ISSN: 0167-2738</identifier><identifier>DOI: 10.1016/j.ssi.2010.06.044</identifier><language>eng</language><subject>Activation energy ; Apatite ; Constants ; Earth ; Electrolytes ; Germanates ; Lanthanum ; Optimization ; Solid oxide fuel cells</subject><ispartof>Solid state ionics, 2010-08, Vol.181 (25-26), p.1189-1196</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c343t-1eb2ee66b61433f2953e95b34937c69afb41cb15b50832c14d9d59e15585b3cc3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Pramana, Stevin S.</creatorcontrib><creatorcontrib>Baikie, Tom</creatorcontrib><creatorcontrib>Kendrick, Emma</creatorcontrib><creatorcontrib>Schreyer, Martin K.</creatorcontrib><creatorcontrib>Slater, Peter R.</creatorcontrib><creatorcontrib>White, T.J.</creatorcontrib><title>Crystal chemistry and optimization of conductivity in 2A, 2M and 2H alkaline earth lanthanum germanate oxyapatite electrolyte polymorphs</title><title>Solid state ionics</title><description>Calcium (La sub(10-x)Ca sub(x)Ge sub(6)O sub(27-x)/2 0 &lt;= x &lt;= 2.57) and barium (La sub(10- x)Ba sub(x)Ge sub(6)O sub(27-x)/2 0 &lt;= nominal x &lt;= 3) doped lanthanum germanate apatites were synthesized by high temperature solid-state sintering. The lattice parameters obtained from Rietveld refinement of powder X-ray diffraction data showed that pseudomorphic transformations from 2A to 2H occurred as the alkaline earth was introduced. The likely appearance of an intervening 2M pseudomorph was not confirmed directly in this study; however, compositionally dependent inflections in cell constants and abrupt changes in oxygen mobility as a function of temperature support its existence, particularly for low alkaline earth contents. Oxygen excess apatites La sub(9)AEGe sub(6)O sub(26.5) (AE = Ca, Sr, Ba) prove most promising as solid oxide fuel cell (SOFC) electrolytes at intermediate temperatures, by delivering the optimal compromise between higher mobile oxygen concentration and lowering of activation energy. In contrast, stoichiometric La sub(8)AE sub(2)Ge sub(6)O sub(26) showed inferior conductivity, because although the activation energy was reduced, the proportion of extrastoichiometric oxygen was negligible. Atomistic modeling suggests that interstitial oxygen is located near (0, 1/2, 1/2) and causes the O3 position to be split statistically into the (0.050, 0.278, 0.587) and (0.084, 0.335, 0.565) sites. 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The lattice parameters obtained from Rietveld refinement of powder X-ray diffraction data showed that pseudomorphic transformations from 2A to 2H occurred as the alkaline earth was introduced. The likely appearance of an intervening 2M pseudomorph was not confirmed directly in this study; however, compositionally dependent inflections in cell constants and abrupt changes in oxygen mobility as a function of temperature support its existence, particularly for low alkaline earth contents. Oxygen excess apatites La sub(9)AEGe sub(6)O sub(26.5) (AE = Ca, Sr, Ba) prove most promising as solid oxide fuel cell (SOFC) electrolytes at intermediate temperatures, by delivering the optimal compromise between higher mobile oxygen concentration and lowering of activation energy. In contrast, stoichiometric La sub(8)AE sub(2)Ge sub(6)O sub(26) showed inferior conductivity, because although the activation energy was reduced, the proportion of extrastoichiometric oxygen was negligible. Atomistic modeling suggests that interstitial oxygen is located near (0, 1/2, 1/2) and causes the O3 position to be split statistically into the (0.050, 0.278, 0.587) and (0.084, 0.335, 0.565) sites. These co-existing locations may facilitate inter-tunnel oxygen transport.</abstract><doi>10.1016/j.ssi.2010.06.044</doi><tpages>8</tpages></addata></record>
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subjects Activation energy
Apatite
Constants
Earth
Electrolytes
Germanates
Lanthanum
Optimization
Solid oxide fuel cells
title Crystal chemistry and optimization of conductivity in 2A, 2M and 2H alkaline earth lanthanum germanate oxyapatite electrolyte polymorphs
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