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 |
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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 <= x <= 2.57) and barium (La sub(10- x)Ba sub(x)Ge sub(6)O sub(27-x)/2 0 <= nominal x <= 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. These co-existing locations may facilitate inter-tunnel oxygen transport.</description><subject>Activation energy</subject><subject>Apatite</subject><subject>Constants</subject><subject>Earth</subject><subject>Electrolytes</subject><subject>Germanates</subject><subject>Lanthanum</subject><subject>Optimization</subject><subject>Solid oxide fuel cells</subject><issn>0167-2738</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><recordid>eNotkM1OwzAQhHMAiVJ4AG6-cSHBP7GTHKsKKFIRFzhbjrMhLkkcbBcRnoDHxqWcZnb1abQ7SXJFcEYwEbe7zHuTURxnLDKc5yfJIu6LlBasPEvOvd9hjAUrxSL5WbvZB9Uj3cFgfHAzUmOD7BTMYL5VMHZEtkXajs1eB_NpwozMiOjqBtGnP5RukOrfVW9GQKBc6FCvxtCpcT-gN3CDGlUAZL9mNcW4aKEHHZzt5-inKIN1U-cvktNW9R4u_3WZvN7fvaw36fb54XG92qaa5SykBGoKIEQtSM5YSyvOoOI1yytWaFGpts6JrgmvOS4Z1SRvqoZXQDgvI6U1WybXx9zJ2Y89-CDj2xr6eDTYvZcl5wUluBKRJEdSO-u9g1ZOzgzKzZJgeSha7mQsWh6KlljIWDT7BZlkduQ</recordid><startdate>20100826</startdate><enddate>20100826</enddate><creator>Pramana, Stevin S.</creator><creator>Baikie, Tom</creator><creator>Kendrick, Emma</creator><creator>Schreyer, Martin K.</creator><creator>Slater, Peter R.</creator><creator>White, T.J.</creator><scope>AAYXX</scope><scope>CITATION</scope><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope></search><sort><creationdate>20100826</creationdate><title>Crystal chemistry and optimization of conductivity in 2A, 2M and 2H alkaline earth lanthanum germanate oxyapatite electrolyte polymorphs</title><author>Pramana, Stevin S. ; Baikie, Tom ; Kendrick, Emma ; Schreyer, Martin K. ; Slater, Peter R. ; White, T.J.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c343t-1eb2ee66b61433f2953e95b34937c69afb41cb15b50832c14d9d59e15585b3cc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Activation energy</topic><topic>Apatite</topic><topic>Constants</topic><topic>Earth</topic><topic>Electrolytes</topic><topic>Germanates</topic><topic>Lanthanum</topic><topic>Optimization</topic><topic>Solid oxide fuel cells</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><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><collection>CrossRef</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Solid state ionics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Pramana, Stevin S.</au><au>Baikie, Tom</au><au>Kendrick, Emma</au><au>Schreyer, Martin K.</au><au>Slater, Peter R.</au><au>White, T.J.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Crystal chemistry and optimization of conductivity in 2A, 2M and 2H alkaline earth lanthanum germanate oxyapatite electrolyte polymorphs</atitle><jtitle>Solid state ionics</jtitle><date>2010-08-26</date><risdate>2010</risdate><volume>181</volume><issue>25-26</issue><spage>1189</spage><epage>1196</epage><pages>1189-1196</pages><issn>0167-2738</issn><abstract>Calcium (La sub(10-x)Ca sub(x)Ge sub(6)O sub(27-x)/2 0 <= x <= 2.57) and barium (La sub(10- x)Ba sub(x)Ge sub(6)O sub(27-x)/2 0 <= nominal x <= 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. 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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source | Elsevier ScienceDirect Journals |
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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