Thin Zinc Electrodes Stabilized with Organobromine‐Partnered H2O−Zn−MeOH Cluster Ions for Practical Zinc‐Metal Pouch Cells

Abstract The utilization of thin zinc (Zn) anodes with a high depth of discharge is an effective strategy to increase the energy density of aqueous Zn metal batteries (ZMBs), but challenged by the poor reversibility of Zn electrode due to the serious Zn‐consuming side reactions at the Zn||electrolyte interface. Here, we introduce 2‐bromomethyl‐1,3‐dioxolane (BDOL) and methanol (MeOH) as electrolyte additive into aqueous ZnSO 4 electrolyte. In the as‐formulated electrolyte, BDOL with a strong electron‐withdrawing group (−CH 2 Br) tends to pair with the H 2 O−Zn−MeOH complex, leading to the formation of organobromine‐partnered H 2 O−Zn−MeOH cluster ions. During the Zn electrodeposition process, the formed ZnO‐dominated by‐products induce the polymerization of BDOL monomers, which are previously adsorbed on the electrode. As a result, a uniform dual‐layer SEI with ZnO‐dominated outer layer and polyether‐dominated inner layer is built on the surface of Zn electrode. With such an in situ formed dual‐layer SEI, the Zn||Mg 0.9 Mn 3 O 7 ⋅ 2.7H 2 O pouch cell using a 10‐um Zn anode (corresponding to a low negative to positive areal capacity ratio of 3.56) successfully operated for 300 cycles with a high capacity retention of 86 %, promising a high practical energy density of >120 Wh/kg (based on the total mass of Zn and Mg 0.9 Mn 3 O 7 ⋅ 2.7H 2 O).