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Thermally and Electrochemically Driven Topotactical Transformations in Sodium Layered Oxides NaxVO2
journal contribution
posted on 2016-02-05, 00:00 authored by Christophe Didier, Marie Guignard, Matthew R. Suchomel, Dany Carlier, Jacques Darriet, Claude DelmasPhase diagrams and structural transformations
in the complex NaxVO2 system
have been studied using
electrochemical (de)intercalation and in situ and operando high resolution
synchrotron powder diffraction. Starting from O′3-Na1/2VO2 obtained by sodium electrochemical deintercalation
of O3-NaVO2, the structural details of irreversible and
reversible thermally driven transformations to P′3 and P3 type
structures are presented. Subsequently, these P′3-NaxVO2 phases provide a platform for operando
studies exploring the NaxVO2 phase diagram as a function of sodium electrochemical (de)intercalation.
In this system, three single phase domains have been found: a line
phase P′3-Na1/2VO2, one solid solution
for 0.53 ≤ x ≤ 0.55 characterized by
an incommensurate modulated structure, and a second solid solution
for 0.63 ≤ x ≤ 0.65 with a defective
structure resulting from a random stack of O′3 and P′3
layers. With further sodium intercalation (x >
0.65),
the structure irreversibly transforms to the starting parent phase
O3-NaVO2. This work reveals new details about the diverse
structural polymorphs found in sodium layered oxides used as electrode
battery materials and the transitional pathways between them as a
function of temperature and composition.
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Keywords
functionsodium electrochemical deintercalationSodium Layered Oxides NaxVO 2Phase diagramsresolution synchrotron powder diffractionelectrode battery materialssodium electrochemicalNaxVO 2 systemTopotactical TransformationstransformationP 3 type structuresphase domainssodium intercalationNaxVO 2 phase diagramoperando studies
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