Elucidating the local structure of Li1+xAlxTi2–x(PO4)3 and Li3AlxTi2–x(PO4)3 (x = 0, 0.3) via total scattering

Chambers, Matthew S.; Liu, Jue; Borkiewicz, Olaf J.; Llopart, Kevin; Sacci, Robert L.; Veith, Gabriel M.

doi:10.1039/d4qi01545b

Title: Elucidating the local structure of Li_1+xAl_xTi_2–x(PO₄)₃ and Li₃Al_xTi_2–x(PO₄)₃ (x = 0, 0.3) via total scattering

Journal Article · 27 September 2024 · Inorganic Chemistry Frontiers (Online)

DOI: https://doi.org/10.1039/d4qi01545b · OSTI ID:2474754

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Li_1+xAl_xTi_2–x(PO₄)₃ (LATP) and Li₃Al_xTi_2–x(PO₄)₃ (x = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10^–3 S cm^–1 and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li_1+xAl_xTi_2–x(PO₄)₃ showing near-zero thermal expansion along the a axis while Li₃Al_xTi_2–x(PO₄)₃ exhibits polynomial positive thermal expansion along the a axis and polynomial negative thermal expansion along the c axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li_1+xAl_xTi_2–x(PO₄)₃ and Li₃Al_xTi_2–x(PO₄)₃ (x = 0, 0.3). We show that the PO₄ and TiO₆ polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along a in Li_1+xAl_xTi_2–x(PO₄)₃ and moving as whole units in Li₃Al_xTi_2–x(PO₄)₃. The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. Finally, this suggests that phosphate-based framework materials beyond LATP would also be a good material space to explore for new Li-ion (and other ion-) conducting materials.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). A Next Generation Synthesis Center (GENESIS); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0019212; AC02-06CH11357

OSTI ID:: 2474754

Journal Information:: Inorganic Chemistry Frontiers (Online), Journal Name: Inorganic Chemistry Frontiers (Online) Journal Issue: 21 Vol. 11; ISSN 2052-1553

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Elucidating the local structure of Li_1+xAl_xTi_2–x(PO₄)₃ and Li₃Al_xTi_2–x(PO₄)₃ (x = 0, 0.3) via total scattering