Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors

Zhou, Laidong; Zhang, Qiang; Nazar, Linda F.

doi:10.1021/acs.chemmater.2c02343

Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors

Journal Article · Tue Oct 25 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c02343· OSTI ID:1896963

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Univ. of Waterloo, ON (Canada); Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here, we report on a new family of halide-deficient and Li-rich argyrodite fast-ion conductors, Li_6+xPS_5+x(Cl/Br/I)_1–x (0 ≤ x ≤ 0.85). Exploration of the influence of aliovalent anion substitution in Li₆PS₅X (X = Cl, Br, I)–using a combination of high-resolution powder neutron diffraction and electrochemical impedance spectroscopy–reveals that aliovalent anion substitution induces higher Li-ion concentration and Li site disorder, and creates S^2–/I^– anion site disorder on the 4a site. In the series Li_6+xPS_5+xI_1–x (0 ≤ x ≤ 0.4), the resulting conductivity for Li_6.4PS_5.4I_0.6 (0.13 mS·cm^–1) represents almost a 100-fold increase over that of the parent phase, Li₆PS₅I (0.0033 mS·cm^–1), and establishes one of the first fast-ion conducting argyrodite thiophosphate iodides. For Cl-argyrodites, the ionic conductivity decreases a little with lower halide-content but ionic conductivity for the Br-argyrodites is almost unchanged. Overall, all Cl/Br-argyrodites Li₆+xPS_5+x(Cl/Br)_1–x (0 ≤ x ≤ 0.75) with a low halide content exhibit surprisingly high ionic conductivities > 1 mS·cm^–1 despite a very low degree of sulfur/halogen anion site disorder. Our findings highlight the importance of attaining a disordered Li-ion sublattice and sulfur/halogen anion site disorder (anionic charge homogeneity) in argyrodites, where Li ions occupy high energy sites and activate concerted ion migration that drives the ionic conductivity.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1896963

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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