Thermodynamic, Kinetic, and Transport Contributions to Hydrogen Evolution Activity and Electrolyte-Stability Windows for Water-in-Salt Electrolytes.

Concentrated water-in-salt electrolytes (WiSEs) are used in aqueous batteries and to control electrochemical reactions for fuel production. The hydrogen evolution reaction is a parasitic reaction at the negative electrode that limits cell voltage in WiSE batteries and leads to self-discharge, and affects selectivity for electrosynthesis. Mitigating and modulating these processes is hampered by a limited fundamental understanding of HER kinetics in WiSEs. Here, we quantitatively assess how thermodynamics, kinetics, and interface layers control the apparent HER activities in 20 m LiTFSI. When the LiTFSI concentration is increased from 1 to 20 m, an increase in proton activity causes a positive shift in the HER equilibrium potential of 71 mV. The exchange current density, , derived from the HER branch for 20 m LiTFSI in 98% purity (0.56 ± 0.05 μA/cm), however, is 8 times lower than for 20 m LiTFSI in 99.95% (4.7 ± 0.2 μA/cm) and 32 times lower than for 1 m LiTFSI in 98% purity (18 ± 1 μA/cm), demonstrating that the WiSE's impurities and concentration are both central in significantly suppressing HER kinetics. The ability and applicability of the reported methods are extended by examining additional WiSEs formulations made of acetates and nitrates.