Liquid Springs from Wettable Materials

Conventional liquid springs enable storage of energy in the form of interfacial tension at forcibly wetted lyophobic surfaces. The pressure–volume work performed to compress the liquid into a poorly wettable porous medium is recovered during spontaneous expulsion when pressure falls below the capillary pressure characteristic of a given system. Our study explores generalizations to easily wettable materials where liquid infiltration is opposed solely by steric hindrance exerted on liquid molecules in micro-sized pores. The concept is exemplified in molecular simulations of prototypical model systems with methanol intruding narrow slits between hydrocarbon or graphene surfaces. While these materials show significant wetting propensities at macroscopic interfaces with liquid methanol, substantial compression is required to wet molecular-sized pores barely accommodating a monolayer of liquid molecules. The observed O(103) bar intrusion pressures secure stored energy densities competitive with supercapacitors and amenable to improvement. Wall–liquid attraction and small pore diameters lead to intrusion–expulsion pathways along cooperative-adsorption isotherms. The process avoids abrupt liquid/vapor transitions and associated nucleation barriers, responsible for cycle hysteresis in experiments with water in hydrophobic capillaries. Using open ensemble (Grand Canonical) Monte Carlo sampling, we identify the range of porosities supporting reversible energy storage/recovery operation in lyophilic media; the results can assist with the design of molecular spring devices with competitive storage and power capacities in pragmatic contexts.