Comparative analysis of DFT-vdW vs. Coulomb energies for configurational space of layered cathode material at different delithiation levels

¹ Samara Center for Theoretical Materials Science, Samara University, Samara, Russia
² Samara Center for Theoretical Materials Science, Samara State Technical University, Samara, Russia

^* Corresponding author: pavelzolotarev@sctms.ru

Published online: 4 February 2019

Abstract

Doping and intercalation ion disordering complicate drastically computer modeling of cathode material properties and behavior during charge-discharge processes. For layered cathode material, parameters of the energetically favored entries of compositional/configurational spaces (CCS) are known to correlate well with the CCS mean values. For the CCS (20760 configurations) of commercially used Li_1-xNi_0.8Co_0.15Al_0.05O₂, a comparative analysis of electrostatic energies and those obtained using first-principles calculations was performed. Based on the Coulomb energy values, the CCS subgroups containing energetically favorable configurations (ca. 25% of the total number of CCS entries) can be identified reliably for Li deficiencies x ≤ 0.5. Further delithiation results in discrepancies between the title methods demonstrating a limited applicability of the simplified selection procedure. The most apparent reason for this is dispersion interaction which can significantly influence structure behavior and shift energetic properties of the layered cathode materials at high lithium deintercalation levels.