The Structural and Electrochemical Impact of Li and Fe Site Substitution in LiFePO4

被引：62

作者：

Omenya, Fredrick ^{[1
]}

Chernova, Natasha A. ^{[2
]}

Wang, Qi ^{[2
,3
]}

Zhang, Ruibo ^{[2
]}

Whittingham, M. Stanley ^{[1
,2
,4
]}

机构：

[1] SUNY Binghamton, Dept Chem, Binghamton, NY 13902 USA

[2] SUNY Binghamton, Inst Mat Res, Binghamton, NY 13902 USA

[3] Brookhaven Natl Lab, Upton, NY 11973 USA

[4] SUNY Stony Brook, Dept Chem, Northeastern Ctr Chem Energy Storage, Stony Brook, NY 11794 USA

来源：

CHEMISTRY OF MATERIALS | 2013年 / 25卷 / 13期

关键词：

olivine; site substitution; Li electrochemistry; sarcopside; PHOSPHO-OLIVINES; VANADIUM; CATHODE; PERFORMANCES; IRON;

D O I：

10.1021/cm401293r

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 crystal structure and delithiation mechanism of Li-site substituted LiFePO4 have been revealed by investigation of supervalent V3+ substitution. The combined X-ray and neutron powder diffraction data analysis surprisingly shows that the substituting aliovalent vanadium ions occupy the Fe site while some of the Fe resides at the Li site, probably as sarcopside, which leads to an increase in the unit cell volume. Such substitution reduces the miscibility gap at room temperature and also significantly lowers the solid solution formation temperature in the two-phase region. The effect of the phase diagram modification results in improved kinetics, leading to better rate performance. Such substitution, however, significantly lowers the LiFePO4 capacity at moderate current densities.

引用

页码：2691 / 2699

页数：9

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