An intuitive and efficient method for cell voltage prediction of lithium and sodium-ion batteries

Abstract

The voltage delivered by rechargeable Lithium-and Sodium-ion batteries is a key parameter to qualify the device as promising for future applications. Here we report a new formulation of the cell voltage in terms of chemically intuitive quantities that can be rapidly and quantitatively evaluated from the alkaliated crystal structure with no need of first-principles calculations. The model, which is here validated on a wide series of existing cathode materials, provides new insights into the physical and chemical features of a crystal structure that influence the material potential. In particular, we show that disordered materials with cationic intermixing must exhibit higher potentials than their ordered homologues. The present method is utilizable by any solid-state chemist, is fully predictive and allows rapid assessement of material potentials, thus opening new directions for the challenging project of material design in rechargeable batteries.

Electrode potential and activation energy of sodium transition-metal oxides as cathode materials for sodium batteries: A first-principles investigation

“…They argued that the larger potential was accompanied with a weaker Fe-O bonding (the lower redox couple) and the stronger X-O bonding through the inductive effect. Furthermore, a novel formulation to predict the battery potential suggests that the higher potential can link to the lower TM-d energy (the lower redox levels) for a given ligand, and that the electrons involved in the redox process mainly come from both the TM and ligand atomic orbitals in their antibonding electronic levels [56]. The present results give further confirmation of the conclusion of these previous works.…”

Influence of polymorphism on the electrochemical behavior of M Sb negative electrodes in Li/Na batteries

“…In electrochemistry, the degree of ionicity of the MÀSb interacting networks is now the dominant parameter governing the redox mechanism, the relative M-sites energies and the battery voltage [45]. To investigate this parameter as well as the impact of Li/Na substitutions onto the electrochemical behaviours of the M 3 Sb phases, Madelung constants are valuable tools.…”

Comparison of computational methods for the electrochemical stability window of solid-state electrolyte materials

“…Equation (8) is identical to the general relation for the A-insertion potential of electro-active battery materials. [18][19][20] In general, the stable SSE composition A n M corresponds to a stoichiometry where all constituting ions are formally in an electronic closed-shell configuration. Consequently, SSE materials have a band gap E LUMO AnM − E HOMO AnM > 0 and are electronic isolators as required for their function as electrolyte.…”