Charge density and redox potential of LiNiO2 using ab initio diffusion quantum Monte Carlo

Abstract

Electronic structure of layered LiNiO2 has been controversial despite numerous theoretical and experimental reports regarding its nature. We investigate the charge densities, lithium intercalation potentials and Li diffusion barrier energies of LixNiO2 (0.0 < x < 1.0) system using a truly ab-initio method, diffusion quantum Monte Carlo (DMC). We compare the charge densities from DMC and density functional theory (DFT) and show that local and semi-local DFT functionals yield spin polarization densities with incorrect sign on the oxygen atoms. 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 p-d hybridization between the Ni-O atoms, yielding accurate lithium intercalation voltages, polarization densities and reaction barriers.

References in corpus (14)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• Continuum variational and diffusion quantum Monte Carlo calculations
• QMCPACK : An open source ab initio Quantum Monte Carlo package for the electronic structure of atoms, molecules, and solids
• Beyond the locality approximation in the standard diffusion Monte Carlo method
• Evaluating transition-metal oxides within DFT-SCAN and SCAN+U frameworks for solar thermochemical applications
• Magnetism and structure of LixCoO2 and comparison to NaxCoO2
• Accurate Cathode Properties of LiNiO2, LiCoO2, and LiMnO2 Using the SCAN Meta-GGA Density Functional
• Electronic phase diagram of the layered cobalt oxide system, LixCoO2 (0.0 <= x <= 1.0)
• Phase Stability of TiO${}_2$ Polymorphs from Diffusion Quantum Monte Carlo
• Excitation energies from diffusion Monte Carlo using selected Configuration Interaction nodes
• Wave functions for quantum Monte Carlo calculations in solids: Orbitals from density functional theory with hybrid exchange-correlation functionals
• Structural Stability and Defect Energetics of ZnO from Diffusion Quantum Monte Carlo
• Perturbatively selected configuration-interaction wave functions for efficient geometry optimization in quantum Monte Carlo

Cited by in corpus (7)

• Oxygen Hole Formation Controls Stability in LiNiO${}_2$ Cathodes: DFT Studies of Oxygen Loss and Singlet Oxygen Formation in Li-Ion Batteries
• A first-principles Quantum Monte Carlo study of two-dimensional (2D) GaSe
• Prediction of Li intercalation voltages in rechargeable battery cathode materials: effects of exchange-correlation functional, van der Waals interactions, and Hubbard $U$
• Compton scattering study of strong orbital delocalization in a LiNiO${}_2$ cathode
• Optimization strategies developed on NiO for Heisenberg exchange coupling calculations using projector augmented wave based first-principles DFT+U+J
• A pathway towards high throughput Quantum Monte Carlo simulations for alloys: A case study of two-dimensional (2D) $Ga{S}_{x}S{e}_{1-x}$
• First-principles analysis of the interplay between electronic structure and volume change in colquiriite compounds during Li intercalation