Journal
JOURNAL OF POWER SOURCES
Volume 317, Issue -, Pages 74-80Publisher
ELSEVIER
DOI: 10.1016/j.jpowsour.2016.03.101
Keywords
Lithium-ion batteries; Li-rich cathode material; Ti doping; Stabilized capacity; Rate performance; Li vacancies
Funding
- National 973 Program of China [2015CB251100]
- National Natural Science Foundation of China [51372268]
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Lithium-rich manganese-based layer-structured oxides (xLi(2)MnO(3)center dot(1-x)LiNi1/3Co1/3Mn1/3O2) have attracted great attention for their potential applications as cathode materials of high energy-density lithium ion batteries. However, these oxides suffer from inferior cycling and poor rate capability due to presence of the Li2MnO3 phase. Herein, the Li+ ions in the Li-layer of the Li1.2Mn0.54Co0.13Ni0.13O2 (or 0.5Li(2)MnO(3)center dot 0.5LiNi(1/3)Co(1/3)Mn(1/3)O(2)) are partially substituted with aliovalent Ti4+ ions to improve its long-term cycling stability and rate performance. The obtained oxide (Li1.2-xTixMn0.54Co0.13Ni0.13O2, x = 2.5%) exhibits an initial capacity of 320 mAh g(-1) and a capacity retention of 71% after 300 cycles as well as good rate performance. In addition, although Ti doping cannot prevent the transformation from the layered to the spinel-like phase, it stabilizes the structure of the spinel-like phase below 3.0 V. Based on first-principles calculations and performance evaluation, these improvements are attributed to the Ti doping induced enhancement in conductivity, diffusion, activation energy of Mn migration and Ti-O bonding. This novel design may furthermore open a door for the synthesis of lithium-rich materials with high rate performance. (C) 2016 Elsevier B.V. All rights reserved.
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