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Download fileFormation Mechanism of β‑Li3PS4 through Decomposition of Complexes
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posted on 2021-04-29, 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 Tadanagaβ-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.