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

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

doi:10.1039/d4qi01545b

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

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

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

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. 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.

Original language	English
Pages (from-to)	7648-7666
Number of pages	19
Journal	Inorganic Chemistry Frontiers
Volume	11
Issue number	21
DOIs	https://doi.org/10.1039/d4qi01545b
State	Published - Sep 27 2024

Funding

The authors thank Katie Browning for providing advice with producing large pellets for the solid-state synthesis of Li1+xAlxTi2−x(PO4)3 (x = 0, 0.3). The authors also thank Rebecca McAuliffe for assisting with sample preparation at 11-ID-B and for providing feedback on an early draft of this manuscript. 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 manuscript has been authored by UT-Battelle, LLC under Contract no. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide 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 (https://energy.gov/downloads/doepublic-access-plan). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to NOMAD on proposal number IPTS-30563.1. The authors thank Katie Browning for providing advice with producing large pellets for the solid-state synthesis of LiAlTi(PO) (x = 0, 0.3). The authors also thank Rebecca McAuliffe for assisting with sample preparation at 11-ID-B and for providing feedback on an early draft of this manuscript. 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 manuscript has been authored by UT-Battelle, LLC under Contract no. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide 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 ( https://energy.gov/downloads/doepublic-access-plan ). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to NOMAD on proposal number IPTS-30563.1. 1+x x 2−x 4 3

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

abstract = "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. 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.",

author = "Chambers, \{Matthew S.\} and Jue Liu and Borkiewicz, \{Olaf J.\} and Kevin Llopart and Sacci, \{Robert L.\} and Veith, \{Gabriel M.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

month = sep,

day = "27",

doi = "10.1039/d4qi01545b",

language = "English",

volume = "11",

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journal = "Inorganic Chemistry Frontiers",

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T1 - Elucidating the local structure of Li1+xAlxTi2−x(PO4)3 and Li3AlxTi2−x(PO4)3 (x = 0, 0.3) via total scattering

AU - Chambers, Matthew S.

AU - Liu, Jue

AU - Borkiewicz, Olaf J.

AU - Llopart, Kevin

AU - Sacci, Robert L.

AU - Veith, Gabriel M.

PY - 2024/9/27

Y1 - 2024/9/27

N2 - 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. 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.

AB - 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. 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.

UR - https://www.scopus.com/pages/publications/85205928565

U2 - 10.1039/d4qi01545b

DO - 10.1039/d4qi01545b

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SN - 2052-1553

VL - 11

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EP - 7666

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

IS - 21

ER -

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

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