Intrinsic Defects in LiMn2O4: First-Principles Calculations

Xu Li; Jianchuan Wang; Shiwei Zhang; Lixian Sun; Weibin Zhang; Feng Dang; Hans J Seifert; Yong Du

doi:10.1021/acsomega.1c01162

Intrinsic Defects in LiMn₂O₄: First-Principles Calculations

ACS Omega. 2021 Aug 12;6(33):21255-21264. doi: 10.1021/acsomega.1c01162. eCollection 2021 Aug 24.

Authors

Xu Li¹, Jianchuan Wang¹, Shiwei Zhang¹, Lixian Sun², Weibin Zhang³, Feng Dang³, Hans J Seifert⁴, Yong Du¹

Affiliations

¹ State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China.
² Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China.
³ Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), Shandong University, Jinan 250061, China.
⁴ Institute for Applied Materials-Applied Materials Physics, Karlsruhe Institute of Technology, Karlsruhe 76344, Germany.

Abstract

Spinel LiMn₂O₄ has attracted wide attention due to its advantages of a high-voltage plateau, good capacity, environmental friendliness, and low cost. Due to different experimental synthesis methods and conditions, there are many intrinsic point defects in LiMn₂O₄. By means of first-principles calculations based on a reasonable magnetic configuration, we studied the formation energies, local structures, and charge compensation mechanism of intrinsic point defects in LiMn₂O₄. The formation energies of defects under the assumed O-rich equilibrium conditions were examined. It was found that O, Li, and Mn vacancies, Mn and Li antisites, and Li interstitial could appear in the lattice at some equilibrium conditions, but Mn interstitial is hard to form. The charge was compensated mainly by adjusting the oxidation state of Mn around the defect, except for the defects at the 8a Wyckoff site. The binding energies between point defects were calculated to shed light on the clustering of point defects. Furthermore, the diffusion of Li ions around the defects was discussed. Cation antisites led to a decrease of the Li diffusion barrier but O vacancy caused an increase of the barrier. This study provides theoretical support for understanding point defects in spinel LiMn₂O₄.