Polarization-Induced Breaching of the Liquid/Liquid Interface Formed with Water-in-Salt Electrolytes The solvation properties of water-in-salt electrolytes (WiSEs) have been extensively studied by spectroscopic and computational means and were shown to impart them with unique chemical and physical properties when compared to more classical superconcentrated aqueous solutions. More specifically, the formation of ionic aggregates in solutions containing a large concentration of TFSI anions was shown to alter the water and anion reactivity at electrochemical interfaces, often improving the performance of aqueous rechargeable batteries. However, insights into the role of the WiSE solvation structure on ion transfer at electrochemical interfaces are scarce. Herein, interfaces between two immiscible electrolytes (ITIESs) are used to study the energetics for ion transfer between aqueous LiCl and LiTFSI solutions and dichloroethane. Combining electrochemical measurements at microinterfaces with metadynamics molecular dynamics (MD) simulations, the effect of solvation properties on the energy for transferring Li+ and Cl–/TFSI– ions across the liquid/liquid interface was studied. While increasing the LiCl concentration increases the amount of ion pairs, it only marginally impacts the ion transfer energy. Instead, using large LiTFSI concentrations at which ionic aggregates are formed, ion transfer across the liquid/liquid interface shows a unique behavior that departs from that observed for polarizable or nonpolarizable interfaces. Ions do not freely cross the interface, with a transfer energy found to be ≈8–10 kcal/mol. However, upon polarization, ionic aggregates are found to breach the liquid/liquid interface, locally mixing both solutions. We believe that such a finding calls for reevaluating our current understanding of ion transfer across chemical interfaces in superconcentrated electrolytes, including liquid/liquid interfaces used in membrane-less electrochemical systems.

Excited to see this work coming out @jacs.acspublications.org. Congrats Lihao on showing the unique transfer mechanism of ionic aggregates forming in Water-in-salt electrolytes across a liquid/liquid interface, with breaching of the interface upon polarization
pubs.acs.org/doi/10.1021/...

Extrinsic and Intrinsic Factors Governing the Electrochemical Oxidation of Propylene in Aqueous Solutions The electrochemical synthesis of commodity chemicals such as epoxides and glycols offers a sustainable alternative to conventional methods that involve hazardous chemicals. Efforts to improve the yiel...

Really glad to see this work finally out. Congrats Taegyu (and collaborators), studying active sites for propylene oxidation on Pd-based catalysts and the effect of cell/electrode design on Faradaic efficiency. pubs.acs.org/doi/10.1021/... @bostoncollege.bsky.social @jacs.acspublications.org

Polarization-induced breaching of liquid/liquid interface formed with water-in-salt electrolytes The solvation properties of water-in-salt-electrolytes (WiSE) have been extensively studied by spectroscopic and computational means, and were shown to impart them with unique chemical and physical pr...

Nice work Lihao! Studying ion transfer across liquid/liquid interfaces using water-in-salt electrolyte, demonstrating polarization-induced breaching of the interface by ionic aggregates, unlike ion pairs forming with "classical" superconcentrated aqueous systems
chemrxiv.org/engage/chemr...

Investigating Lithium Ordering and Electronic Evolutions in Wadsley–Roth Phases The development of new materials for fast-charging lithium-ion batteries is critical to meet the growing demand for energy storage technologies. As a result of their high capacity and high-rate capabi...

Glad to see Everett's work finally out. Everett has pushed our lab capabilities by developing entropic potential and in situ electronic conductivity measurements and revealed Li ordering during intercalation in Wadsley-Roth block phase materials
pubs.acs.org/doi/10.1021/...