Defects, Lithium Mobility and Tetravalent Dopants in the Li 3 NbO 4 Cathode Material

The defect processes of oxides such as self-diffusion impact their performance in electrochemical devices such as batteries and solid oxide fuel cells. The performance of lithium ion batteries can be improved by increasing the Li-ion diffusion. In that respect Li 3 NbO 4 is identified as a positive electrode material for rechargeable lithium ion batteries. Here, we employ static atomistic scale simulations to examine the defect properties, doping behaviour and lithium ion migration paths in Li 3 NbO 4 . The present calculations show a correct reproduction of experimentally observed crystal structure of Li 3 NbO 4 . The Li-Nb anti-site defect is found to be the dominant intrinsic defect process suggesting that a small concentration of Li on Nb sites and Nb on Li sites is present. Vacancy assisted long range lithium diffusion paths were examined and our calculations reveal that the lowest activation energy (1.13 eV) migration path is two dimensional forming a zig-zag shape. Subvalent doping by Ge on the Nb site is thermodynamically favourable process and a potential strategy to incorporate extra Li in the form of Li interstitial in Li 3 NbO 4 . The results presented herein can motivate further experimental work for the development of Li 3 NbO 4 based batteries.