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Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material

By Jianming Zheng (341590), Pinghong Xu (1650208), Meng Gu (627187), Jie Xiao (113647), Nigel D. Browning (1420711), Pengfei Yan (306846), Chongmin Wang (1277376) and Ji-Guang Zhang (1487506)


Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, the voltage fading mechanism in these materials as well as its relationships to fundamental structural changes is far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li­[Li<sub>0.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>]­O<sub>2</sub>) during cycling for samples prepared by the hydrothermal assisted (HA) method. It is found that the transformation pathway of the LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that the LMR cathode prepared by the HA approach experiences a phase transformation from the layered structure (initial <i>C</i>2/<i>m</i> phase transforms to <i>R</i>3̅<i>m</i> phase after activation) to a LT-LiCoO<sub>2</sub> type defect spinel-like structure (with the <i>Fd</i>3̅<i>m</i> space group) and then to a disordered rock-salt structure (with the <i>Fm</i>3̅<i>m</i> space group). The voltage fade can be well correlated with Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like and disordered rock-salt structures. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that permits Li percolation in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a large quantity of oxygen vacancies, a significant decrease in the Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn–Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change provides unique understanding of the voltage fade and capacity degradation mechanisms in the LMR cathode. The results also inspire us to further enhance the reversibility of the LMR cathode via improved surface structural stability

Topics: Biophysics, Biochemistry, Medicine, Cell Biology, Genetics, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, voltage, LMR cathode, Li ion insertion, HA approach experiences, capacity degradation mechanisms, phase transformation pathway, Mn valence change
Year: 2015
DOI identifier: 10.1021/cm5045978.s001
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Provided by: FigShare
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