Interfacial Chemistry in Aqueous Lithium-Ion Batteries with Dilute Aqueous Electrolytes: A Case Study with V2O5

Abstract

Aqueous lithium ion batteries (ALIBs) are promising candidates for large-scale energy storage systems, benefiting from the intrinsic safe and environmentally friendly properties of aqueous electrolytes. However, its practical application is impeded due to the narrow electrochemical stability windows (ESWs) of aqueous electrolytes. Despite that increasing electrolyte concentration can achieve a wide ESW with the protection of SEI layer, it brings numerous disadvantages induced by excessive salt as well. Therefore, understanding the SEI formation mechanism and further widening the ESWs of dilute aqueous electrolytes are critical for the breakthrough of next-generation ALIBs.Herein, the interphase chemistry of V2O5 electrode with dilute aqueous electrolyte was systematic investigated by conducting various Operando characterizations with LMO||V2O5 cell system. Dynamic SEI, which consists of Li2CO3, LiF and V2O4, was formed during charge and disappeared during the following discharge, which is strongly affected by electrolyte pH fluctuation. Moreover, its evolution process is reversible during cycling. There are several impacts affect the pH fluctuation during cycling. First, V2O5 dissolution, which turns electrolyte into acidic before cycling, and is aggravated by electrolyte concentration decrease. Second, proton/hydronium ion insertion, which takes place on electrode surface in dilute electrolyte, while it is suppressed by concentration increase due to reduced proton concentration. Third, the redox reaction of dissolved V2O5, which is controlled by both potential and electrolyte pH change according to the V-H2O poubaix diagram. Along with the anode potential decrease and the alkalinisation of electrolyte, V2O4 is formed on anode surface by the reduction of HV10O28 5- and V4O12 4- and this reduction process further produces hydroxide ion into electrolyte. Last, the carbon oxidation, which takes place on cathode side during charge and on anode side during the final discharge. Therefore, the acidification of electrolyte during cycling is detrimental to SEI stability in aqueous electrolytes. This systematic research work provides new perspectives to the understanding of the interphase chemistry evolution in aqueous Li-ion batteries using dilute electrolytes, which guides the building of effective SEI layer in aqueous Li-ion batteries and beyond. Figure 1