第一原理计算过渡金属掺杂尖晶石型LiMn <sub>2</sub>O<sub>4</sub>的电子结构

宁连才; 吴金平; 周成刚; 姚淑娟; 程寒松

第一原理计算过渡金属掺杂尖晶石型LiMn ₂O₄的电子结构

宁连才^{1, 2,},
吴金平^{1, 2},
周成刚^{1, 2},
姚淑娟^{1, 2},
程寒松^{1, 2}

1.
中国地质大学材料科学与化学工程学院, 湖北武汉 430074
2.
中国地质大学理论化学与计算材料科学研究所, 湖北武汉 430074

基金项目:

中国地质大学优秀青年教师资助计划 cugQnl0519

详细信息

作者简介:
宁连才(1980-), 男, 硕士研究生, 主要从事锂离子电池材料的理论计算与实验研究工作. E-mail: nlcaiwm@126.com

中图分类号: TM912
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出版历程
- 刊出日期: 2006-05-25

First Principles Calculation of Electronic Structure of Spinel Manganese Oxide Doping with Transition Metal

NING Lian-cai^{1, 2
,},
WU Jin-ping^{1, 2},
ZHOU Cheng-gang^{1, 2},
YAO Shu-juan^{1, 2},
CHENG Han-song^{1, 2}

1.
Faculty of Material Science and Chemical Engineering, China University of Geosciences, Wuhan 430074, China
2.
Institute of Theoretical Chemistry and Computational Materials Science, China University of Geosciences, Wuhan 430074, China

摘要

摘要: 尽管对过渡金属掺杂锰酸锂后放电平台的升高现象有众多实验研究, 但对其机理的研究却鲜见报道.采用第一原理的密度泛函理论, 计算了过渡金属M(M=Ti、Cr、Fe、Co、Ni、Cu、Zn)掺杂尖晶石型LiMn₂O₄的电子结构, 并以此分析放电平台的升高机理.电子态密度分析发现由于M-3d能带的诱导作用, 出现了新的O-2p能带, 而锂脱出时获得的电子, 主要是由费米能级附近O-2p能带提供的.当过渡金属M由Ti变化到Zn时, M-3d能带逐渐向低能量的方向移动, 新的O-2p能带出现的位置也随之下移, 当Li脱出时, 需要更多的能量才能从低能量的O-2p能带上获得电子, 因而体系能够获得较高的嵌入电压.
- 尖晶石型LIMN₂O₄ /
- 电子结构 /
- 第一原理 /
- 掺杂
Abstract: Although there has been intensive research on improving the discharge voltage plateau of lithium manganese oxide doped by transition metals, there is a lack of corresponding studies on the improvement mechanism. In this paper, we investigate the electronic structure of spinel manganese oxide doping with transition metal M (M=Ti, Cr, Fe, Co, Ni, Cu, Zn) by first principles calculation based on the density functional theory. The calculated density of states indicates that a new O-2p band induced by the M-3d band appears at the exact position of the M-3d band itself. The compensating electrons are removed from the O-2p levels neighboring the Fermi level when the Li ion is removed. The position of the M-3d band shifts gradually to the low energy direction as M varies from Ti to Zn in the transition metal row of the periodic table, and the position of the new O-2p band also shifts downward following the M-3d band. The withdrawal of lithium electrons from this low O-2p band will result in high cell voltage.
- spinel manganese oxide /
- electronic structure /
- first principles /
- doping

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图 1 尖晶石型LiMn₂O₄的晶胞结构模型

Fig. 1. Cell configuration of spinel manganese oxide

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图 2 LiM_0.125Mn_1.875O₄(M=Ti、Cr、Fe、Co、Ni、Cu、Zn)中Mn-3d、M-3d和O-2p的分态密度(PDOS)

Fig. 2. Partial density of states of Mn-3d band, M-3d band and O-2p band in LiM_0.125Mn_1.875O₄(M=Ti, Cr, Fe, Co, Ni, Cu, Zn)

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图 3 局部放大的LiM_0.125Mn_1.875O₄(M=Ti、Cr、Fe、Co、Ni、Cu、Zn)中Mn-3d、M-3d和O-2p的分态密度(PDOS)

Fig. 3. Enlarged partial density of states of Mn-3d band, M-3d band and O-2p band in LiM_0.125Mn_1.875O₄(M=Ti, Cr, Fe, Co, Ni, Cu, Zn)

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