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

ABSTRACT: 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.

SUBMITTER: Chen Y

PROVIDER: S-EPMC10990923 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

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

Chen Yu Y Lun Zhengyan Z Zhao Xinye X Koirala Krishna Prasad KP Li Linze L Sun Yingzhi Y O'Keefe Christopher A CA Yang Xiaochen X Cai Zijian Z Wang Chongmin C Ji Huiwen H Grey Clare P CP Ouyang Bin B Ceder Gerbrand G

Nature materials 20240202 4

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 ...[more]

PMID: 38308087

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Project description:On the basis of ab initio computer simulations, pre-melting phenomena have been suggested to occur in the elastic properties of hexagonal close-packed iron under the conditions of the Earth's inner core just before melting. The extent to which these pre-melting effects might also occur in the physical properties of face-centred cubic metals has been investigated here under more experimentally accessible conditions for gold, allowing for comparison with future computer simulations of this material. The thermal expansion of gold has been determined by X-ray powder diffraction from 40 K up to the melting point (1337 K). For the entire temperature range investigated, the unit-cell volume can be represented in the following way: a second-order Grüneisen approximation to the zero-pressure volumetric equation of state, with the internal energy calculated via a Debye model, is used to represent the thermal expansion of the 'perfect crystal'. Gold shows a nonlinear increase in thermal expansion that departs from this Grüneisen-Debye model prior to melting, which is probably a result of the generation of point defects over a large range of temperatures, beginning at T/Tm > 0.75 (a similar homologous T to where softening has been observed in the elastic moduli of Au). Therefore, the thermodynamic theory of point defects was used to include the additional volume of the vacancies at high temperatures ('real crystal'), resulting in the following fitted parameters: Q = (V0K0)/γ = 4.04 (1) × 10-18 J, V0 = 67.1671 (3) Å3, b = (K0' - 1)/2 = 3.84 (9), θD = 182 (2) K, (vf/Ω)exp(sf/kB) = 1.8 (23) and hf = 0.9 (2) eV, where V0 is the unit-cell volume at 0 K, K0 and K0' are the isothermal incompressibility and its first derivative with respect to pressure (evaluated at zero pressure), γ is a Grüneisen parameter, θD is the Debye temperature, vf, hf and sf are the vacancy formation volume, enthalpy and entropy, respectively, Ω is the average volume per atom, and kB is Boltzmann's constant.

Dataset Information

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

Publications

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

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