Energetic Stability and Its Role in the Mechanism of Ionic Transport in NASICON-Type Solid-State Electrolyte Li 1+ x Al x Ti 2- x (PO 4 ) 3

We apply high-temperature oxide melt solution calorimetry to assess the thermodynamic properties of the material Li Al Ti (PO ) , which has been broadly recognized as one of the best Li-ion-conducting solid electrolytes of the NASICON family. The experimental results reveal large exothermic enthalpi...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2021-05, Vol.12 (18), p.4400-4406
Main Authors: Abramchuk, Mykola, Voskanyan, Albert A, Arinicheva, Yulia, Lilova, Kristina, Subramani, Tamilarasan, Ma, Qianli, Dashjav, Enkhtsetseg, Finsterbusch, Martin, Navrotsky, Alexandra
Format: Article
Language:English
Subjects:
Chemistry
Materials Science
Physics
Science & Technology - Other Topics
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Summary:We apply high-temperature oxide melt solution calorimetry to assess the thermodynamic properties of the material Li Al Ti (PO ) , which has been broadly recognized as one of the best Li-ion-conducting solid electrolytes of the NASICON family. The experimental results reveal large exothermic enthalpies of formation from binary oxides (Δ ) and elements (Δ ) for all compositions in the range 0 ≤ ≤ 0.5. This indicates substantial stability of Li Al Ti (PO ) , driven by thermodynamics and not just kinetics, during long-term battery operation. The stability increases with increasing Al content. Furthermore, the dependence of the formation enthalpy on the Al content shows a change in behavior at = 0.3, a composition near which the Li conductivity reaches the highest values. The strong correlation among thermodynamic stability, ionic transport, and clustering is a general phenomenon in ionic conductors that is independent of the crystal structure as well as the type of charge carrier. Therefore, the thermodynamic results can serve as guidelines for the selection of compositions with potentially the highest Li conductivity among different NASICON-type series with variable dopant contents.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.1c00925