Off-stoichiometry, Vacancy Trapping and Pseudo-irreversible First-cycle Capacity in LiNiO2

We demonstrate that the ubiquitous off-stoichiometry of LiNiO2 in the form of Li_{1-z}Ni_{1+z}O2 slows the kinetics of the material both by diminishing the number of charge carriers and increasing the length of diffusion paths. Excess Ni in the Li layer, Ni_{Li}, exerts an attractive potential on Li vacancies, lowering their energy with respect to defect-free regions. This attractive field extends over a radius of two lattice sites and also considerably lowers the barrier for a Li vacancy to approach the defect, effectively making Ni_{Li} a sink for lithium vacancies. A similar argument can be made for divacancies, which are split by Ni_{Li} and pinned in the form of single vacancies. In addition to pinning effects, which could vary depending on the state of charge, Ni_{Li} also constitutes an obstacle to Li migration, because it is rather immobile and does not undergo site-exchange with an adjacent Li vacancy.