The Role of Ni and Co in Suppressing O‐Loss in Li‐Rich Layered Cathodes
Édouard Boivin, Niccoló Guerrini, Robert A. House, J. G. Lozano, Liyu Jin, Gregory J. Rees, James Somerville, Christian Kuß, Matthew R. Roberts, Peter G. Bruce
Abstract
Abstract Lithium‐rich transition metal cathodes can deliver higher capacities than stoichiometric materials by exploiting redox reactions on oxygen. However, oxidation of O 2− on charging often results in loss of oxygen from the lattice. In the case of Li 2 MnO 3 all the capacity arises from oxygen loss, whereas doping with Ni and/or Co leads to the archetypal O‐redox cathodes Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 and Li[Li 0.2 Ni 0.13 Co 0.13 Mn 0.54 ]O 2 , which exhibit much reduced oxygen loss. Understanding the factors that determine the degree of reversible O‐redox versus irreversible O‐loss is important if Li‐rich cathodes are to be exploited in next generation lithium‐ion batteries. Here it is shown that the almost complete eradication of O‐loss with Ni substitution is due to the presence of a less Li‐rich, more Ni‐rich (nearer stoichiometric) rocksalt shell at the surface of the particles compared with the bulk, which acts as a self‐protecting layer against O‐loss. In the case of Ni and Co co‐substitution, a thinner rocksalt shell forms, and the O‐loss is more abundant. In contrast, Co doping does not result in a surface shell yet it still suppresses O‐loss, although less so than Ni and Ni/Co doping, indicating that doping without shell formation is effective and that two mechanisms exist for O‐loss suppression.