Material design of new lithium ionic conductor, thio-LISICON, in the Li2S-P2S5 system
Material design of new lithium ionic conductor, thio-LISICON, in the Li2S-P2S5 system
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DOI：
10.1016/j.ssi.2004.02.025
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发表时间：
2004-05-31
影响因子：
3.2
通讯作者：
Kanno, R
中科院分区：
文献类型：
--
作者：
Murayama, M;Sonoyama, N;Kanno, R
在Li_2S-P_2S_5二元体系中发现了一种新的锂离子导体--硫代锂超离子导体（thio-LISICON，Lithium Superlonic Conductor）;在700 ℃下合成了组成范围为0.0 ≤ x ≤ 0.27的新固溶体Li_3 + 5xP_1-xS_4，并通过X射线衍射测量进行了表征。用交流阻抗法和循环伏安法研究了其电学和电化学性质。在Li 3 + 5xP 1-xS-4中x = 0.065的固溶体成员在27 ℃下显示出1.5 × 10（-4）S cm（-1）的最高电导率值，具有可忽略的电子电导率和22 U mol（-1）的活化能，这是高离子导电状态的特征。由于P5+部分取代Li+而在Li 3 PS4中产生额外的锂离子，导致离子电导率的大幅增加。在所检查的固溶体范围内，对于组成Li 3 PS4（在Li 3 + 5xP 1-xS 4中x = 0.0）和Li4P0.8S4（在Li 3 + 5xP 1-xS 4中x = 0.2）获得最小电导率;该电导率行为类似于具有通式LixM 1-yMy'S-4（M = Si，Ge，并且M' = P，Al，Zn，Ga，Sb）的其它硫代-LISICON族。基于导电行为和结构考虑，讨论了导电机制和材料设计概念。(C)2004 Elsevier B. V.保留所有权利。
A new lithium ionic conductor of the thio-LISICON (LIthium Superlonic CONductor) family was found in the binary Li2S-P2S5 system; the new solid solution with the composition range 0.0 less than or equal to x less than or equal to 0.27 in Li3+5xP1-xS4 was synthesized at 700 degreesC 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-x S-4 showed the highest conductivity value of 1.5 x 10(-4) S cm(-1) at 27 degreesC with negligible electronic conductivity and the activation energy of 22 U 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'S-4 (M = Si, Ge, and M' = P, Al, Zn, Ga, Sb). Conduction mechanism and the material design concepts are discussed based on the conductlion behavior and the structure considerations. (C) 2004 Elsevier B.V. All rights reserved.