Computational
and Experimental Investigation of Ti
Substitution in Li<sub>1</sub>(Ni<sub><i>x</i></sub>Mn<sub><i>x</i></sub>Co<sub>1–2<i>x</i>–<i>y</i></sub>Ti<sub><i>y</i></sub>)O<sub>2</sub> for
Lithium Ion Batteries
- Publication date
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Abstract
Aliovalent
substitutions in layered transition-metal cathode materials
has been demonstrated to improve the energy densities of lithium ion
batteries, with the mechanisms underlying such effects incompletely
understood. Performance enhancement associated with Ti substitution
of Co in the cathode material Li<sub>1</sub>(Ni<sub><i>x</i></sub>Mn<sub><i>x</i></sub>Co<sub>1–2<i>x</i></sub>)O<sub>2</sub> were investigated using density functional theory
calculations, including Hubbard-U corrections. An examination of the
structural and electronic modifications revealed that Ti substitution
reduces the structural distortions occurring during delithiation due
to the larger cation radius of Ti<sup>4+</sup> relative to Co<sup>3+</sup> and the presence of an electron polaron on Mn cations induced
by aliovalent Ti substitution. The structural differences were found
to correlate with a decrease in the lithium intercalation voltage
at lower lithium concentrations, which is consistent with quasi-equilibrium
voltages obtained by integrating data from stepped potential experiments.
Further, Ti is found to suppress the formation of a secondary rock
salt phase at high voltage. Our results provide insights into how
selective substitutions can enhance the performance of cathodes, maximizing
the energy density and lifetime of current Li ion batteries