Cation Ordering of Zr-Doped LiNiO2 Cathode for Lithium-Ion Batteries

Ordered occupation of Ni ions in the Li ion layer (and vice versa) was observed in 0.4 mol % Zr-doped LiNiO2 with R (3) over barm structure. Although cation mixing is prevalent in LiNiO2 and in other Ni-rich layered cathodes, cation ordering (Li and Ni) has not been previously reported in the as-prepared or fully discharged states. First principles calculations verified that low-level doping of LiNiO2 with Zr can energetically promote the observed cation ordering. Contrary to previous beliefs, antisite defects (or cation mixing), whose presence is unequivocally justified by the cation ordering, had hardly any negative effect on the electrochemical performance of LiNiO2; both pristine and Zr-doped LiNiO2 delivered 247.5 and 246.5 mAh g(-1) respectively, with a Coulombic efficiency of 97%. The capacity retention after 100 cycles was improved by increasing Zr doping to 81% from 74%. The improved cycling stability was attributed to the particle morphology being conducive to Li migration and relieving the deeply charged LirNiO(2) of its inherent structural instability.This work was mainly supported by the Global Frontier R&D Program (2013M3A6B1078875) on Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, Information & Communication Technology (ICT) and the Human Resources Development program (No. 20154010200840) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Trade, Industry and Energy. QZ. and P.K. acknowledge the North-German Supercomputing Alliance (HLRN) for providing HPC resources