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

Timrov, Iurii  
•
Kotiuga, Michele  
•
Marzari, Nicola  
February 21, 2023
Physical Chemistry Chemical Physics

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 LixMn2O4 and LixMn1.5Ni0.5O4 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.

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