Halide sublattice dynamics drive Li-ion transport in antiperovskites

Robert L. Sacci; Tyler H. Bennett; Hong Fang; Kee Sung Han; Michelle Lames; Vijayakumar Murugesan; Puru Jena; Jagjit Nanda

doi:10.1039/d2ta02598a

Halide sublattice dynamics drive Li-ion transport in antiperovskites

Robert L. Sacci, Tyler H. Bennett, Hong Fang, Kee Sung Han, Michelle Lames, Vijayakumar Murugesan, Puru Jena, Jagjit Nanda

Energy Storage & Conversion

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

6 Scopus citations

Abstract

Here, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li_3−xOH_xX, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (∼250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li₂OHCl_0.37Br_0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10⁻⁶vs. 4.9 × 10⁻⁸ S cm⁻¹ (Li₂OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.

Original language	English
Pages (from-to)	15731-15742
Number of pages	12
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	29
DOIs	https://doi.org/10.1039/d2ta02598a
State	Published - Jul 13 2022

Funding

Experiment design, data analysis, and manuscript preparation (RLS) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering. Synthesis (THB and JN) was supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. P. J. acknowledges partial support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-96ER45579. H. F. was supported from U.S. Department of Energy (Award No. DE-EE0008865). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The NMR characterization part of the work is supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, and Basic Energy Sciences. The NMR work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory. 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 non-exclusive, 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/doe-public-access-plan). Experiment design, data analysis, and manuscript preparation (RLS) were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering. Synthesis (THB and JN) was supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. P. J. acknowledges partial support by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-96ER45579. H. F. was supported from U.S. Department of Energy (Award No. DE-EE0008865). This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The NMR characterization part of the work is supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, and Basic Energy Sciences. The NMR work was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a DOE User Facility sponsored by the Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory. 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 non-exclusive, 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/doe-public-access-plan ).

Funders	Funder number
DOE Public Access Plan
Joint Center for Energy Storage Research
United States Government
U.S. Department of Energy
Office of Science	DE-AC02-05CH11231
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
Biological and Environmental Research
Pacific Northwest National Laboratory	DE-AC05-00OR22725
Division of Materials Sciences and Engineering	DE-EE0008865, DE-FG02-96ER45579
Environmental Molecular Sciences Laboratory

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10.1039/d2ta02598a

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title = "Halide sublattice dynamics drive Li-ion transport in antiperovskites",

abstract = "Here, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li3−xOHxX, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (∼250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li2OHCl0.37Br0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10−6vs. 4.9 × 10−8 S cm−1 (Li2OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.",

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AU - Sacci, Robert L.

AU - Bennett, Tyler H.

AU - Fang, Hong

AU - Han, Kee Sung

AU - Lames, Michelle

AU - Murugesan, Vijayakumar

AU - Jena, Puru

AU - Nanda, Jagjit

PY - 2022/7/13

Y1 - 2022/7/13

N2 - Here, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li3−xOHxX, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (∼250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li2OHCl0.37Br0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10−6vs. 4.9 × 10−8 S cm−1 (Li2OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.

AB - Here, we resolve how proton dynamics and halide mixing enhance or impede ionic conduction in protonated lithium antiperovskites (pLiAP) at compositions near the eutectic points of the halide salts. As a material class, pLiAPs of the form Li3−xOHxX, (X = Cl, Br) show vast compositional design freedom; however, the resulting properties are susceptible to synthesis and processing methodologies. Proton incorporation and halide mixing stabilize the perovskite cubic phase at low temperatures (<50 °C) and using halide mixtures near the eutectic points (∼250 to 300 °C) offer possibilities of lower temperature and faster synthesis and processing conditions (<1 h). Mixed-halide compositions such as Li2OHCl0.37Br0.63 lead to a 30-fold improvement in room temperature ionic conductivity of a single halide structure, 1.5 × 10−6vs. 4.9 × 10−8 S cm−1 (Li2OHCl). We combine infrared spectroscopy and nuclear magnetic resonance with first-principles density functional theory calculations to deconvolute halide mixing effects from local proton dynamics on Li-ion transport. In contrast to what has been supposed, our findings suggest that the halide sublattice dynamics, besides the OH rotation, correlate strongly with the fast-ion conduction at high temperatures.

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Halide sublattice dynamics drive Li-ion transport in antiperovskites

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