Abstract
The structural chemistry of the solid ion-conducting LixLa2/3-x/3TiO3 (LLTO) is rich with various polymorphs related to atomic segregation. We explored the LLTO reaction pathway from various structurally related precursors (La2LiO3H, Li2TiO3, and Li4Ti5O12), focusing on the effects of LLTO-like structural motifs in precursors using a combination of experimental and computational techniques. Density functional theory (DFT) calculations revealed that the failure of syntheses to produce LLTO below 1300 °C is due to the presence of multiple competing low-energy phases that result in competitive byproduct formation. In all syntheses where T = 1300 °C, LLTO was the sole product; however, varying phase fractions of I4/mcm and P4/nbm polymorphs and double-perovskite P4/mmm can be obtained depending on the synthesis route. This is an unusual result as at 1300 °C, LLTO should only be the ideal cubic Pm-3m perovskite structure, yet there appears to be a memory effect from the different precursors resulting in the unique phase selectivity and stabilization.
Original language | English |
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Pages (from-to) | 1197-1213 |
Number of pages | 17 |
Journal | Chemistry of Materials |
Volume | 36 |
Issue number | 3 |
DOIs | |
State | Published - Feb 13 2024 |
Funding
The authors thank Katie Browning of the Oak Ridge National Laboratory for aiding with the synthesis of LaLiOH. This work was also supported as part of GENESIS: A Next Generation Synthesis Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DESC0019212. This work used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doepublic-access-plan ). 2 3 The authors thank Katie Browning of the Oak Ridge National Laboratory for aiding with the synthesis of La2LiO3H. This work was also supported as part of GENESIS: A Next Generation Synthesis Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DESC0019212. This work used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doepublic-access-plan).