Unlocking Li superionic conductivity in face-centred cubic oxides via face-sharing configurations.

Oxides with a face-centred cubic (fcc) anion sublattice are generally not considered as solid-state electrolytes as the structural framework is thought to be unfavourable for lithium (Li) superionic conduction. Here we demonstrate Li superionic conductivity in fcc-type oxides in which face-sharing Li configurations have been created through cation over-stoichiometry in rocksalt-type lattices via excess Li. We find that the face-sharing Li configurations create a novel spinel with unconventional stoichiometry and raise the energy of Li, thereby promoting fast Li-ion conduction. The over-stoichiometric Li-In-Sn-O compound exhibits a total Li superionic conductivity of 3.38 × 10-4 S cm-1 at room temperature with a low migration barrier of 255 meV. Our work unlocks the potential of designing Li superionic conductors in a prototypical structural framework with vast chemical flexibility, providing fertile ground for discovering new solid-state electrolytes.

Description

Acknowledgements: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the US Department of Energy (DOE) under contract no. DE-AC02-05CH11231. Z.L. and C.P.G. were supported by an ERC Advanced Investigator Grant for C.P.G. (EC H2020 ERC 835073). The computational analysis was performed using computational resources sponsored by the DOE’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory. Computational resources were also provided by the Extreme Science and Engineering Discovery Environment, supported by the National Science Foundation grant number ACI1053575, and the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science and the US DOE under contract no. DE-AC02-05CH11231. This research also used the Lawrencium computational cluster resource provided by the IT Division at Lawrence Berkeley National Laboratory (supported by the Director, Office of Science, Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231). Work at the Molecular Foundry, Lawrence Berkeley National Laboratory was supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract no. DE-AC02-05CH11231. This work used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used the mail-in program at Beamline 17-BM of the Advanced Photon Source, a US DOE Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The TEM work was carried at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the US DOE under the contract DE-AC05-76RL01830.

Funder: EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council); doi: https://doi.org/10.13039/100010663

Keywords

34 Chemical Sciences, 3406 Physical Chemistry, 40 Engineering, 51 Physical Sciences, 4016 Materials Engineering

Journal Title

Nat Mater

Journal ISSN

1476-1122
1476-4660

Volume Title

23

Publisher

Springer Science and Business Media LLC

Publisher DOI

https://doi.org/10.1038/s41563-024-01800-8

Rights

Attribution 4.0 International

Sponsorship

European Commission Horizon 2020 (H2020) ERC (835073)

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. ZL and CPG were supported by an ERC Advanced Investigator Grant for Prof. Clare Grey (EC H2020 ERC 835073). The computational analysis was performed using computational resources sponsored by the DOE’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory. Computational resources were also provided by the Extreme Science and Engineering Discovery Environment (XSEDE), supported by National Science Foundation grant number ACI1053575, and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science and the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This research also used the Lawrencium computational cluster resource provided by the IT Division at Lawrence Berkeley National Laboratory (Supported by the Director, Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under contract no. DE-AC02-05CH11231). Work at the Molecular Foundry, LBNL was supported by the Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This work used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used the mail-in program at Beamline 17-BM 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. The TEM work was carried at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility-24-sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the U.S. DOE under the Contract DE-AC05- 76RL01830.

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