Aqueous electrolytes at the charged graphene Surface: Electrode-Electrolyte coupling

Electrochemical energy sources support the growth in performance and portability of consumer electronics. Further sustainable development assumes an atomistically precise understanding of how the electrolyte binds to the electrode in the charged and uncharged states of the supercapacitors and Li-ion batteries. The present work investigates electrode–electrolyte interactions at the cathode using ab initio molecular dynamics simulations and representative energy-minimized ion-molecular configurations. Graphene is chosen as a material for the cathode, whereas the aqueous solutions of LiCl, NaCl, and KCl are model electrolytes. The study reveals a few fundamentally new physical insights regarding the performance of a supercapacitor. First, the graphene-ions coordination regularities are qualitatively different at charged and uncharged cathode. It is, therefore, essential to account for the effect of charging when studying the physical chemistry of supercapacitors. Second, the energy capacity offered by the aqueous Na-ion electrolyte is worse than those of the aqueous Li-ion and K-ion electrolytes. This observation is a result of an interplay between the dehydration energies and adsorption energies at the cathode energies. Third, the role of cation-solvent binding represents a cornerstone contribution to the capacity of an energy storage device in addition to the well-recognized cation-cathode binding thermodynamics. The reported results are fundamentally important to thoughtfully designing electrolyte compositions and electrode materials for supercapacitors and alkali-ion batteries.