Constructing Cyclic Hydrogen Bonding to Suppress Side Reactions and Dendrite Formation on Zinc Anodes

Abstract The high electrochemical reactivity of H 2 O molecules and zinc metal results in severe side reactions and dendrite formation on zinc anodes. Here we demonstrate that these issues can be addressed by using N‐hydroxymethylacetamide (NHA) as additives in 2 M ZnSO 4 electrolytes. The addition of NHA molecules, acting as both a hydrogen bond donor and acceptor, enables the formation of cyclic hydrogen bonding with H 2 O molecules. This interaction disrupts the existing hydrogen bonding networks between H 2 O molecules, hindering proton transport, and containing H 2 O molecules within the cyclic hydrogen bonding structure to prevent deprotonation. Additionally, NHA molecules show a preference for adsorption on the (101) crystal surface of zinc metal. This preferential adsorption reduces the surface energy of the (101) plane, facilitating the homogeneous Zn deposition along the (101) direction. Thus, the NHA enables Zn||Zn symmetric cell with a cycle lifespan of 1100 hours at 5 mA cm −2 and Zn||Cu asymmetric cell with a high Coulombic efficiency over 99.5 %. Moreover, the NHA‐modified Zn||AC zinc ion hybrid capacitor is capable of sustaining 15000 cycles at 2 A g −1 . This electrolyte additive engineering presents a promising strategy to enhance the performance and broaden the application potential of zinc metal‐based energy storage devices.