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

Journal Article · · Inorganic Chemistry Frontiers (Online)
DOI:https://doi.org/10.1039/d4qi01545b· OSTI ID:2474754
 [1];  [1];  [2];  [1];  [1];  [1]
  1. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
+ Show Author Affiliations
Li1+xAlxTi2–x(PO4)3 (LATP) and Li3AlxTi2–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 Li1+xAlxTi2–x(PO4)3 showing near-zero thermal expansion along the a axis while Li3AlxTi2–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 Li1+xAlxTi2–x(PO4)3 and Li3AlxTi2–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 Li1+xAlxTi2–x(PO4)3 and moving as whole units in Li3AlxTi2–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.
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
Alternate ID(s):
OSTI ID: 2449664
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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