Shift of redox potential and kinetics in Lix(MnyFe1-y)PO4

被引：103

作者：

Kobayashi, Genki ^{[1
]}

Yamada, Atsuo ^{[1
]}

Nishimura, Shin-ichi ^{[1
]}

Kanno, Ryoji ^{[1
]}

Kobayashi, Yo ^{[2
]}

Seki, Shiro ^{[2
]}

Ohno, Yasutaka ^{[2
]}

Miyashiro, Hajime ^{[2
]}

机构：

[1] Tokyo Inst Technol, Interdisciplinary Grad Sch Sci & Engn, Dept Elect Chem, Midori Ku, Yokohama, Kanagawa 2268502, Japan

[2] Cent Res Inst Elect Power Ind, Tokyo 2018511, Japan

来源：

JOURNAL OF POWER SOURCES | 2009年 / 189卷 / 01期

关键词：

Olivine; Cathode; Iron; Phosphate; Lithium; Battery; LITHIUM BATTERIES; ELECTRODE MATERIALS; OLIVINE; CATHODES; MN; FE;

D O I：

10.1016/j.jpowsour.2008.07.085

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The relatively high redox potential in the olivine-type LiMPO4 (M = Mn, Fe, Co, Ni) materials has largely been explained by the M-O-P inductive effect which increases the ionic character of transition metal atoms. Here, we identify the additional perturbative effect that slightly but systematically shifts the redox potential. The substitution of iron by manganese in the olivine LiMPO4 framework raises both of the Fe3+/Fe2+ and Mn3+/Mn2+ redox potentials by similar to 0.1 V. The overall volume expansion upon Mn substitution in the whole Li-x(MnyFe1-y)PO4 system possibly increases the average metal-oxide bond length and hence the ionicity of each transition metal. The voltage shift in a single cell is small but should be significant in a larger-scale battery where there exist a large number of series connections. The kinetic shift for each of the Fe3+/Fe2+ and Mn3+/Mn2+ redox reactions is also investigated. (C) 2008 Elsevier B.V. All rights reserved.

引用

页码：397 / 401

页数：5

共 13 条

[1] Olivine LiCoPO4 as 4.8 V electrode material for lithium batteries [J].