Prediction of Li intercalation voltages in rechargeable battery cathode materials: effects of exchange-correlation functional, van der Waals interactions, and Hubbard $U$

Abstract

Quantitative predictions of the Li intercalation voltage and of the electronic properties of rechargeable battery cathode materials are a substantial challenge for first-principles theory due to the possibility of (1) strong correlations associated with localized transition metal $d$ electrons and (2) significant van der Waals (vdW) interactions in layered systems, both of which are not accurately captured by standard approximations to density functional theory (DFT). Here, we perform a systematic benchmark of electronic structure methods based on the widely-used generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE) and the new strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for battery cathode materials. Studying layered Li${}_x$TiS${}_2$, Li${}_x$NiO${}_2$, and Li${}_x$CoO${}_2$, olivine Li${}_x$FePO${}_4$, and spinel Li${}_x$Mn${}_2$O${}_4$, we compute the voltage, crystal structure, and electronic structure with and without extensions to incorporate on-site Hubbard interactions and vdW interactions. Within pure DFT (i.e., without corrections for on-site Hubbard interactions), SCAN is a significant improvement over PBE for describing cathode materials, decreasing the mean absolute voltage error by more than 50%. Although explicit vdW interactions are not critical and in cases even detrimental when applied in conjunction with SCAN, Hubbard $U$ corrections are still in general necessary to achieve reasonable agreement with experiment. We show that no single method considered here can accurately describe the voltage and overall structural, electronic, and magnetic properties (i.e., errors no more than 5% for voltage, volume, band gap, and magnetic moments) of battery cathode materials, motivating a strong need for improved electronic structure approaches for such systems.

References in corpus (31)

• Van der Waals Density Functional for General Geometries
• Van der Waals density functionals applied to solids
• A linear response approach to the calculation of the effective interaction parameters in the LDA+U method
• Efficient implementation of a van der Waals density functional: Application to double-wall carbon nanotubes
• Nonlocal van der Waals density functional: The simpler the better
• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• First-principles prediction of redox potentials in transition-metal compounds with LDA+U
• Hubbard-corrected DFT energy functionals: the LDA+U description of correlated systems
• van der Waals forces in density functional theory: The vdW-DF method
• SCAN+rVV10: A promising van der Waals density functional
• The electronic structure and band gap of LiFePO4 and LiMnPO4
• Regularized SCAN functional
• Comparative first-principles studies of prototypical ferroelectric materials by LDA, GGA, and SCAN meta-GGA
• Rungs 1 to 4 of DFT Jacob's ladder: extensive test on the lattice constant, bulk modulus, and cohesive energy of solids
• Performance of the strongly constrained and appropriately normed density functional for solid-state materials
• Calibrating transition metal energy levels and oxygen bands in first principles calculations: accurate prediction of redox potentials and charge transfer in lithium transition metal oxides
• Evaluating transition-metal oxides within DFT-SCAN and SCAN+U frameworks for solar thermochemical applications
• Phase Separation in Li${}_x$FePO${}_4$ Induced by Correlation Effects
• Accurate Cathode Properties of LiNiO2, LiCoO2, and LiMnO2 Using the SCAN Meta-GGA Density Functional
• Cation- and vacancy-ordering in Li_xCoO_2
• Antiferromagnetic Ground State of La${}_2$CuO${}_4$: A Parameter-free Ab Initio Description
• Electronic phase diagram of the layered cobalt oxide system, LixCoO2 (0.0 <= x <= 1.0)
• Synthesis and properties of CoO2, the x = 0 end member of the LixCoO2 and NaxCoO2 systems
• Energetics and cathode voltages of LiMPO${}_4$ olivines (M = Fe, Mn) from extended Hubbard functionals
• Electronic Correlations in CoO2, the Parent Compound of Triangular Cobaltates
• Enhancing the efficiency of density functionals with a novel iso-orbital indicator
• Magnetic and Electronic Properties of Li${}_x$CoO${}_2$ Single Crystals
• Charge density and redox potential of LiNiO2 using ab initio diffusion quantum Monte Carlo
• Measurement of electron correlations in LixCoO2 (x=0.0 - 0.35) using 59Co nuclear magnetic resonance and nuclear quadrupole resonance techniques
• Electronic phase diagram of LixCoO2 revisited with potentiostatically de-intercalated single crystals
• Compositional phase stability of strongly correlated electron materials within DFT+$U$

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• Lattice and Electronic properties of VO${}_2$ with the SCAN(+$U$) approach
• Anomalous Reversal of Stability in Mo-containing Oxides: A Difficult Case Exhibiting Sensitivity to DFT+U and Distortion
• Stability and electronic properties of layered NaMnO2 using the SCAN(+U)
• Assessing the accuracy of compound formation energies with quantum Monte Carlo
• Comparison of SCAN+U and r2SCAN+U for Charge Density Wave Instability and Lattice Dynamics in CuTe