Charge Density and Redox Potential of LiNiO2 Using Ab Initio Diffusion Quantum Monte Carlo

Kayahan Saritas, Jeffrey C. Grossman, Eric R. Fadel, Boris Kozinsky

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

We investigate the charge densities, lithium intercalation potentials, and Li-diffusion barrier energies of LixNiO2 (0.0 < x < 1.0) system using the diffusion quantum Monte Carlo (DMC) method. We find an average redox potential of 4.1(2) eV and a Li-diffusion barrier energy of 0.39(3) eV with DMC. Comparisoin of the charge densities from DMC and density functional theory (DFT) and show that local and semilocal DFT functionals yield spin polarization densities with an incorrect sign on the oxygen atoms. The SCAN functional and Hubbard-U correction improves the polarization density around Ni and O atoms, resulting in smaller deviations from the DMC densities. DMC accurately captures the many-body nature of Ni−O bonding, hence yielding accurate lithium intercalation voltages, polarization densities, and reaction barriers.

Original languageEnglish
Pages (from-to)5893-5901
Number of pages9
JournalJournal of Physical Chemistry C
Volume124
Issue number11
DOIs
StatePublished - Mar 19 2020
Externally publishedYes

Funding

The funding for this work was provided by Robert Bosch LLC, Cambridge, MA. We thank the computational resources provided by the National Energy Research Scientific Computing Center (NERSC), the Extreme Science and Engineering Discovery Environment (XSEDE), and the Oak Ridge Leadership Computing Facility (OLCF).

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