Unraveling the effects of inter-site Hubbard interactions in spinel Li-ion cathode materials

Abstract

Accurate first-principles predictions of the structural, electronic, magnetic, and electrochemical properties of cathode materials can be key in the design of novel efficient Li-ion batteries. Spinel-type cathode materials Li${}_x$Mn${}_2$O${}_4$ and Li${}_x$Mn${}_{1.5}$Ni${}_{0.5}$O${}_4$ are promising candidates for Li-ion battery technologies, but they present serious challenges when it comes to their first-principles modeling. Here, we use density-functional theory with extended Hubbard functionals - DFT+$U$+$V$ with on-site $U$ and inter-site $V$ Hubbard interactions - to study the properties of these transition-metal oxides. The Hubbard parameters are computed from first-principles using density-functional perturbation theory. We show that while $U$ is crucial to obtain the right trends in properties of these materials, $V$ is essential for a quantitative description of the structural and electronic properties, as well as the Li-intercalation voltages. This work paves the way for reliable first-principles studies of other families of cathode materials without relying on empirical fitting or calibration procedures.

References in corpus (16)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Quantum ESPRESSO toward the exascale
• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• Self-consistent Hubbard parameters from density-functional perturbation theory in the ultrasoft and projector-augmented wave formulations
• HP -- A code for the calculation of Hubbard parameters using density-functional perturbation theory
• Extensive Benchmarking of DFT+U Calculations for Predicting Band Gaps
• Hubbard-corrected density functional perturbation theory with ultrasoft pseudopotentials
• Understanding the electronic and ionic conduction and lithium over-stoichiometry in LiMn${}_2$O${}_4$ spinel
• Ab initio electron-phonon interactions in correlated electron systems
• Accurate electronic properties and intercalation voltages of olivine-type Li-ion cathode materials from extended Hubbard functionals
• Pulay forces in density-functional theory with extended Hubbard functionals: From nonorthogonalized to orthogonalized manifolds
• Optimizing accuracy and efficacy in data-driven materials discovery for the solar production of hydrogen
• Importance of intersite Hubbard interactions in $\beta$-MnO${}_2$: A first-principles DFT+$U$+$V$ study
• Pivotal Role of Intersite Hubbard Interactions in Fe-doped $\alpha$-MnO${}_2$
• Ab initio study of lattice dynamics of group IV semiconductors using pseudohybrid functionals for extended Hubbard interactions

Cited by in corpus (6)

• Orbital-resolved DFT+U for molecules and solids
• Understanding the role of Hubbard corrections in the rhombohedral phase of BaTiO${}_3$
• On-site and inter-site Hubbard corrections in magnetic monolayers: The case of FePS${}_3$ and CrI${}_3$
• First-principles Hubbard parameters with automated and reproducible workflows
• Magnons from time-dependent density-functional perturbation theory and nonempirical Hubbard functionals
• Comparative study of magnetic exchange parameters and magnon dispersions in NiO and MnO from first principles