First-principles prediction of redox potentials in transition-metal compounds with LDA + U -: art. no. 235121
First-principles prediction of redox potentials in transition-metal compounds with LDA + U -: art. no. 235121
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DOI：
10.1103/physrevb.70.235121
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发表时间：
2004-12-01
影响因子：
3.7
通讯作者：
Ceder, G
中科院分区：
文献类型：
--
作者：
Zhou, F;Cococcioni, M;Ceder, G
局部密度近似（LDA）或广义梯度近似（GGA）中的第一原理计算虽然非常成功，但众所周知会低估氧化还原电位，例如锂嵌入过渡金属化合物中的氧化还原电位。我们认为这种不准确性与 LDA/GGA 中电子自相互作用误差缺乏消除有关，并且可以通过使用 DFT+U 方法和 U 参数的自洽评估来改进。我们表明，使用这种方法，可以准确地再现许多过渡金属化合物的实验嵌锂电压，包括橄榄石 LixMPO4 (M=Mn, Fe Co, Ni)、层状 LixMO2 (x=Co, Ni) 和尖晶石状 LixM2O4 (M=Mn, Co)。
First-principles calculations within the local density approximation (LDA) or generalized gradient approximation (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compounds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT+U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the experimental lithium intercalation voltages of a number of transition metal compounds, including the olivine LixMPO4 (M=Mn, Fe Co, Ni), layered LixMO2 (x=Co, Ni) and spinel-like LixM2O4 (M=Mn, Co), can be reproduced accurately.