Applications of the Vienna Ab initio simulation package, DFT and molecular interaction studies for investigating the electrochemical stability and solvation performance of non-aqueous NaMF6 electrolytes for sodium-ion batteries

A Graphical illustration of the electron transport and electronic property of Na+(EC:EMC)PF6- electrolyte analysis with Gaussian and MedeA® VASP. [Display omitted] •Na+(S)MF6- optimised structure is utilised to examine its electronic properties and interpret its FT-IR spectra.•The optical spectra, band structure, and DOS of the most stable Na+(EC:EMC)PF6- electrolyte are simulated using the MedeA - VASP with GGA approach.•When electrophilicity is high, more interaction with EC and EMC in NaMF6 salts is favorable. This interaction also demonstrates that EC, EMC, and DMC have higher electrolyte dissolving capabilities than DEC solvent.•The current research is highly correlated to the database of sodium hexafluorophosphate, and these investigations led in the identification of similar and enhanced stability, conductivity, and redox potential using DFT based B3LYP/631G (d) simulation.•Our findings suggest that sodium-based electrolytes may be non-flammability, high ionic conductivity, high thermal stability and corrosion-resistant. This work uses a DFT-based method to compute the molecule's reduction and oxidation potentials to determine electronic association and provides high accuracy results when comparing the electrochemical stability in an electrolyte's with experimental data. The sodium electrolytes were ordered based on the determined electrochemical potentials of the PF6- anion and Na+ cation interactions with carbonates. Since EC and EMC are more dominating than DMC and DEC according to the data, the solvent solvation model is represented for further investigations as a mix combination. Following research, we get comparable sodium-based electrolytes with similar reactivity that are similar in activity to sodium hexafluorophosphate (NaPF6). Often, variables including free energy, chemical potential, frontier molecular orbitals, molecular electrostatic potential (MEP), hardness, softness, electronegativity and electrophilicity score are used to illustrate the relationship between the stability, redox potential, chemical reactivity and corrosion inhibition of electrolyte analogues. The good solubility in carbonates and chemically active sodium-based electrolytes has been discussed. Using VASP, the optical data of NaPF6 was investigated and band structure and DOS analysis were used to identify and correlate the experimental band gap values. The appropriate delineation of the performance of quantum chemistry simulations to investigate the electronic charac