In silico Based Rank-Order Determination and Experiments on Non-Aqueous Electrolytes for Li-Ion Batteries and Beyond

Electrolytes are an important component of electrochemical energy storage systems and their optimization is critical for emerging beyond lithium ion technologies. Here, an integrated computational-experimental approach is used to rank-order and aid the selection of suitable electrolytes for a Na-ion battery. We present an in silico strategy based on both thermodynamic and kinetic descriptors derived from molecular dynamics simulations to rationally arrive at optimal electrolytes for Na-ion batteries. We benchmarked various electrolytes (pure and binary mixtures of cyclic and acyclic carbonates with NaClO₄ salt) to identify appropriate formulations with the overarching goal of simultaneously enhancing cell performance while meeting safety norms. Fundamental insights from computationally derived thermodynamic and kinetic data considerations coupled with atomistic-level description of the solvation dynamics is used to rank order the various electrolytes. Thermodynamic considerations based on free energy evaluation indicate EC:PC as a top electrolyte formulation under equilibrium conditions. However, kinetic descriptors which are important factors dictating the rate capability and power performance suggest EC:DMC and EC:EMC to be amongst the best formulations. Experimental verification of these optimized formulations was carried out by examining the electrochemical performance of various electrolytes in Na/TiO₂ nanotubes half cells with NaClO₄ salt. Our rate capability studies confirm that EC:DMC and EC:EMC to be the best formulations. These optimized formulations have reversible specific capacities ~180-240 mAh/g whereas the lower ranked electrolytes (EC:DEC) have capacities ~100 mAh/g. The various electrolytes are also evaluated from a safety perspective. Such results suggest encouraging prospects for this approach in the a priori prediction of optimal sodium ion systems with possible screening implications for novel battery formulations.