Nonstochiometry in LiFe0.5Mn0.5PO4: Structural and Electrochemical Properties

被引：20

作者：

Amisse, Robin ^{[1
,2
,3
]}

Hamelet, Stephane ^{[1
]}

Hanzel, Darko ^{[4
]}

Courty, Matthieu ^{[1
]}

Dominko, Robert ^{[2
,3
]}

Masquelier, Christian ^{[1
,2
]}

机构：

[1] Univ Picardie Jules Verne, LRCS, F-80039 Amiens, France

[2] ALISTORE ERI, F-80039 Amiens, France

[3] Natl Inst Chem, SI-1001 Ljubljana, Slovenia

[4] Jozef Stefan Inst, SI-1000 Ljubljana, Slovenia

来源：

JOURNAL OF THE ELECTROCHEMICAL SOCIETY | 2013年 / 160卷 / 09期

关键词：

CRYSTAL-CHEMISTRY; CATHODE MATERIALS; ROOM-TEMPERATURE; LIMPO4; M; LITHIUM; BATTERY; LIFEPO4; FE; 0-LESS-THAN-OR-EQUAL-TO-X-LESS-THAN-OR-EQUAL-TO-1; DIFFRACTION;

D O I：

10.1149/2.068309jes

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

The effect of mild oxidation in air of LiFe1-yMnyPO4 (0 <= y <= 1) powders is studied via in situ and ex situ X-ray diffraction, thermogravimetric analysis and Mossbauer spectroscopy. Structural modifications involve an anisotropic change in the lattice parameters upon heat-treatment with conservation of the olivine-type structure up to similar to 500 degrees C. The extrusion of part of iron in the form of alpha-Fe2O3 is observed, which results in the oxidation of iron in the structure and the creation of vacancies, while Mn remains stable at a +2 oxidation state. Mass gain and unit-cell volume variations upon heat-treatment under air are found to be proportional to y in the pristine composition. In addition, the electrochemical signature of powders annealed at similar to 300 degrees C significantly differs from the stoichiometdc ones. Two solid solution contributions arise from the Fe3+/Fe2+ redox couple, and the Mn3+/Mn2+ reaction upon Li+ electrochemical insertion/extraction is reported for the first time as a solid solution reaction. (C) 2013 The Electrochemical Society.

引用

页码：A1446 / A1450

页数：5

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