Material design of new lithium ionic conductor, thio-LISICON, in the Li2S–P2S5 system |
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Authors: | Masahiro Murayama Noriyuki Sonoyama Atsuo Yamada Ryoji Kanno |
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Institution: | Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Midori, Yokohama, Kanagawa 226-8502, Japan |
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Abstract: | A new lithium ionic conductor of the thio-LISICON (LIthium SuperIonic CONductor) family was found in the binary Li2S–P2S5 system; the new solid solution with the composition range 0.0≤x≤0.27 in Li3+5xP1?xS4 was synthesized at 700 °C and characterized by X-ray diffraction measurements. Its electrical and electrochemical properties were studied by ac impedance and cyclic voltammetry measurements, respectively. The solid solution member at x=0.065 in Li3+5xP1?xS4 showed the highest conductivity value of 1.5×10?4 S cm?1 at 27 °C with negligible electronic conductivity and the activation energy of 22 kJ mol?1 which is characteristic of high ionic conduction state. The extra lithium ions in Li3PS4 created by partial substitution of P5+ for Li+ led to the large increase in ionic conductivity. In the solid solution range examined, the minimum conductivity was obtained for the compositions, Li3PS4 (x=0.0 in Li3+5xP1?xS4) and Li4P0.8S4 (x=0.2 in Li3+5xP1?xS4); this conductivity behavior is similar to other thio-LISICON family with the general formula, LixM1?yMy′S4 (M=Si, Ge, and M′=P, Al, Zn, Ga, Sb). Conduction mechanism and the material design concepts are discussed based on the conduction behavior and the structure considerations. |
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Keywords: | Lithium ionic conductor Thio-LISICON Lithium phosphorus sulfide Lithium solid electrolyte |
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