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Formation Mechanism of β‑Li3PS4 through Decomposition of Complexes

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posted on 29.04.2021, 14:39 authored by Marcela Calpa, Hiroshi Nakajima, Shigeo Mori, Yosuke Goto, Yoshikazu Mizuguchi, Chikako Moriyoshi, Yoshihiro Kuroiwa, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
β-Li3PS4 is a solid electrolyte with high Li+ conductivity, applicable to sulfide-based all-solid-state batteries. While a β-Li3PS4-synthesized by solid-state reaction forms only in a narrow 300–450 °C temperature range upon heating, β-Li3PS4 is readily available by liquid-phase synthesis through low-temperature thermal decomposition of complexes composed of PS43 and various organic solvents. However, the conversion mechanism of β-Li3PS4 from these complexes is not yet understood. Herein, we proposed the synthesis mechanism of β-Li3PS4 from Li3PS4·acetonitrile (Li3PS4·ACN) and Li3PS4·1,2-dimethoxyethane (Li3PS4·DME), whose structural similarity with β-Li3PS4 would reduce the nucleation barrier for the formation of β-Li3PS4. Synchrotron X-ray diffraction clarified that both complexes possess similar layered structures consisting of alternating Li2PS4 and Li+-ACN/DME layers. ACN/DME was removed from these complexes upon heating, and rotation of the PS4 tetrahedra induced a uniaxial compression to form the β-Li3PS4 framework.