Atomic-scale investigation of defects, dopants, and lithium transport in the LiFePO4 olivine-type battery material

被引：989

作者：

Islam, MS ^{[1
]}

Driscoll, DJ ^{[1
]}

Fisher, CAJ ^{[1
]}

Slater, PR ^{[1
]}

机构：

[1] Univ Surrey, Mat Chem Grp, Div Chem, SBMS, Guildford GU2 7XH, Surrey, England

来源：

CHEMISTRY OF MATERIALS | 2005年 / 17卷 / 20期

关键词：

D O I：

10.1021/cm050999v

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：

Key issues relating to intrinsic defects, dopant incorporation, and lithium ion migration in the LiFePO4 electrode material have been investigated using well-established atomistic modeling techniques. Our simulation model shows good reproduction of the observed olivine-type structure of LiFePO4. The most favorable intrinsic defect is the Li-Fe "anti-site" pair in which a Li ion (on the M1 site) and an Fe ion (on the M2 site) are interchanged. This type of anti-site defect or "intersite exchange" has been observed in olivine silicates. The lowest Li migration energy is found for the pathway along the [010] channel, with a nonlinear, curved trajectory between adjacent Li sites. Trends in dopant substitution energetics of a range of cations with charges varying from +2 to +5 are also examined. Low favorable energies are found only for divalent dopants on the Fe site (such as Mn), which is in accord with experimental work. Our results suggest that, on energetic grounds, LiFePO4 is not tolerant to aliovalent doping (e.g., Al, Ga, Zr, Ti, Nb, Ta) on either Li (M1) or Fe (M2) sites.

引用

页码：5085 / 5092

页数：8

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