title: Vacancy-induced MnO6distortion and its impacts on structural transition of Li2MnO3.
abstract: As a new class of high-capacity cathode materials, the Li-rich Mn-based layer-structured xLi2MnO3·(1 - x)LiMO2(M = Ni, Co, Mn, etc.) is a promising candidate for constructing high energy-density Li-ion batteries. Unfortunately, drawbacks such as oxygen evolution, poor rate performance and potential fading during cycling hinder their commercial applications. Migration of the transition metal (Mn) into the Li layer of Li2MnO3and the resultant irreversible structural transition are believed to be responsible for these issues. Therefore, it is essential to explore the driving force for the Mn migration. In this study, we show, starting from understanding the impact of O and Li vacancies on the migration of the Mn atoms by the first-principles molecular dynamics simulation, that Mn migration is closely involved in the breaking and forming of the Mn-O bonds of the MnO6octahedron and its continuous distortion (MnOx, 4 ≤ x ≤ 6). In addition, Mn migration along with the generation of O vacancy lowers the delithiation potential. Inconsistent with conventional beliefs, Mn migration into the Li layer was found to promote, rather than block, Li diffusion in some cases. The mechanism for MnO6distortion provides new insight into understanding the micro mechanism of the layered-to-spinel structural transition and revealing the designing of superior cathode materials.
authors.affiliation: Key Laboratory for Renewable Energy, Chinese Academy of Sciences, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China. zxwang@iphy.ac.cn and School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100190, China and Department of Physics and Astronomy, California State University Northridge, Northridge, California 91330-8268, USA.
authors.forename: Yurui
authors.initials: Y
authors.lastname: Gao
authors.affiliation: Key Laboratory for Renewable Energy, Chinese Academy of Sciences, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China. zxwang@iphy.ac.cn and School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100190, China and Qingdao Industrial Energy Storage Technology Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Ma
authors.affiliation: Key Laboratory for Renewable Energy, Chinese Academy of Sciences, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China. zxwang@iphy.ac.cn and School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Zhaoxiang
authors.identifier: http://orcid.org/0000-0002-1123-6591
authors.initials: Z
authors.lastname: Wang
authors.affiliation: Department of Physics and Astronomy, California State University Northridge, Northridge, California 91330-8268, USA.
authors.forename: Gang
authors.initials: G
authors.lastname: Lu
authors.affiliation: Key Laboratory for Renewable Energy, Chinese Academy of Sciences, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China. zxwang@iphy.ac.cn and School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Liquan
authors.initials: L
authors.lastname: Chen