Energetics of Ion Transport in NASICON-Type Electrolytes

Francisco, Brian E.; Stoldt, Conrad R.; M’Peko, Jean-Claude

doi:10.1021/acs.jpcc.5b03286

Title: Energetics of Ion Transport in NASICON-Type Electrolytes

Journal Article · Mon Jul 13 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b03286· OSTI ID:1225088

Francisco, Brian E. ^[1]; Stoldt, Conrad R. ^[1]; M’Peko, Jean-Claude ^[2]

Univ. of Colorado, Boulder, CO (United States)
Univ. de São Paulo (Brazil)

Herein we report a study on the energetics of ion transport in NASICON-type solid electrolytes. A sol–gel procedure was used to synthesize NASICON-type lithium-ion conductors with nominal compositions Li_1+XAl_XGe_2–X(PO₄)₃ where 0 ≤ X ≤ 0.6. Trends in the conductivity and activation energy, including both enthalpic and entropic contributions, were examined with electrochemical impedance spectroscopy. Physical interpretations of these results are drawn from structural characterizations performed by synchrotron powder X-ray diffraction and Raman spectroscopy. Considering X = 0 → 0.6, we conclude that initial drops in activation energy are driven by a growing Li⁺ population on M2 sites, while later increases in activation energy are driven by changes in average bottleneck size caused by the Al-for-Ge substitution. Values of the entropy of motion are rationalized physically by considering the changing configurational potential of the mobile Li⁺ population with changes in X. We conclude that entropic contributions to the free energy of activation amount to ≤22% of the enthalpic contributions at room temperature. Furthermore, these insights suggest that while entropic contributions are not insignificant, more attention should be paid to lowering the activation energy when designing a new NASICON-type conductor.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; DMR-1231048

OSTI ID:: 1225088

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 29; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 31 works

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Cited By (2)

Structural elucidation of NASICON (Na ₃ Al ₂ P ₃ O ₁₂ ) based glass electrolyte materials: effective influence of boron and gallium Allu, Amarnath R.; Balaji, Sathravada; Illath, Kavya RSC Advances, Vol. 8, Issue 26 https://doi.org/10.1039/c8ra01676c	journal	January 2018
Improving NASICON Sinterability through Crystallization under High-Frequency Electrical Fields Lisenker, Ilya; Stoldt, Conrad R. Frontiers in Energy Research, Vol. 4 https://doi.org/10.3389/fenrg.2016.00013	journal	March 2016

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Title: Energetics of Ion Transport in NASICON-Type Electrolytes

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