Working mechanism of MXene as the anode protection layer of aqueous zinc-ion batteries

In recent years, the research on intrinsically safe aqueous zinc-ion batteries (AZIBs) has gained significant attention. However, the commercialization of AZIBs is hindered because of the formation of dendrites in them and undesired hydrogen evolution reaction (HER) at their anode. MXene is a promising two-dimensional material that can inhibit dendrite growth and undesired HER at the anode when used as a protective layer for the anode in AZIBs. MXene's surface functional groups play a crucial role in this protective function. However, the working mechanisms of these surface functional groups have not been thoroughly understood. Based on first-principles calculations and molecular dynamics simulation, we investigated the mechanisms of MXene with nine surface functional groups, including oxygen and halogen elements, as an anode protection layer. We checked their structural stability, electronic structure, adsorption energy, HER reaction free energy, Zn2+ diffusion energy barriers, coordination number of Zn2+- H2O and diffusion coefficients of Zn2+. The MXene species with -S and -O functional groups exhibit good electrical conductivity and greatly adsorb Zn2+. Conversely, MXene species with halogen-functional groups significantly inhibit HER reactions. MXene materials with -Se functional group have the best desolvation effect (ΔCN = 0.31), while those with -I end group have the fastest ability to diffuse zinc ion. This research provides a theoretical guidance for the design of MXene based anode protection layers, which can help to develop dendrite-free and low side-reaction AZIBs.