Origin of the Electrochemical Stability of Aqueous Concentrated Electrolyte Solutions

The electrochemical stability of an electrolyte solution, its so-called "potential window", is simply determined by the oxidative potential and reductive potential of the solvent, if solutes dissolved in the electrolyte solution are electrochemically stable within the potential window of the solvent. Water is the most conventional solvent in the field of electrochemistry, and its potential window is as narrow as 1.23 V, thermodynamically. Practically, however, the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) need certain overpotentials, which extends the potential windows of aqueous solutions. Besides the catalytic activities of the electrode materials, the properties of aqueous solutions such as hydration structures and salt concentrations also affect the potential window.Recently, aqueous rechargeable lithium batteries (ARLBs) have attracted much attention due to their low cost and safety. However, the working voltage of ARLBs is limited to below 1.5 V due to the narrow potential window of water. Recently, a few papers have discussed the potential window of concentrated aqueous solutions with neutral pH. However, there are still fundamental unanswered questions regarding the pH-dependence of the potential window of water. In this study, the potential window of concentrated electrolyte solutions with neutral pH and the expansion of the potential window were investigated from the viewpoint of the local pH change and water concentration. Here, we shed light on the dependence of the potential window of water on local pH changes and water concentrations. Next, we focused on the water concentration, since the potential windows are determined by the water electrolysis reactions (OER and HER). The potential windows are shown in Fig. 1 as a function of the water concentrations. In this study, the onset potential of the OER/HER was defined when the current density was ± 0.1 mA cm-2 in CVs at 1 mV s-1. There are two clear tendencies in Fig. 1. First, the windows in neutral pH electrolyte solutions (closed symbols in Fig. 1) were obviously wider than those in acidic/alkaline electrolyte solutions (open symbols in Fig. 1), even at a dilute salt concentration (ca. 55 M water concentration). Second, the windows in neutral pH electrolyte solution (closed symbols in Fig. 1) were not affected by the kind of the electrolyte salt, but depended linearly on the water concentration. The windows were expanded when the water concentration decreased, i.e., the electrolyte salt concentrations increased. Potential windows of aqueous solutions were investigated systematically using various salts at different concentrations. Cyclic voltammetry measurements of Pt electrodes revealed two important points. First, the potential window in unbuffered neutral pH solution was broader than that in acidic/alkaline solutions. This expansion of potential windows can be explained by the shift in the reaction potential with local pH changes in the vicinity of the electrode. Second, the potential windows were not affected by electrolyte salts, but rather depended linearly on the water concentration. The difference for OER overpotentials was much larger than that for HER overpotentials. While HER overpotentials were derived from a local pH change, OER overpotentials were derived from both a reduced water concentration and local pH change. This study highlights the importance of these two main factors (water concentration and local pH change) in determining the potential windows of concentrated electrolyte solutions. Figure 1