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Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)₂], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)₂], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology. 

We report on viscous adhesion measurements conducted in sphere-plane geometry between a rigid sphere and soft surfaces submerged in silicone oils. Increasing the surface compliance leads to a decrease in the adhesive strength due to elastohydrodynamic deformation of the soft surface during debonding. The force-displacement and fluid film thickness-time data are compared to an elastohydrodynamic model that incorporates the force measuring spring and finds good agreement between the model and data. We calculate the pressure distribution in the fluid and find that, in contrast to debonding from rigid surfaces, the pressure drop is non-monotonic and includes the presence of stagnation points within the fluid film when a soft surface is present. In addition, viscous adhesion in the presence of a soft surface leads to a debonding process that occurs via a peeling front (located at a stagnation point), even in the absence of solid–solid contact. As a result of mass conservation, the elastohydrodynamic deformation of the soft surface during detachment leads to surfaces that come closer as the surfaces are separated. During detachment, there is a region with fluid drainage between the centerpoint and the stagnation point, while there is fluid infusion further out. Understanding and harnessing the coupling between lubrication pressure, elasticity, and surface interactions provides material design strategies for applications such as adhesives, coatings, microsensors, and biomaterials.