Hydrogen‐Bond‐Mediated Proton Blocking Strategy for Achieving Ultrastable Zinc Anodes

Abstract Aqueous electrolytes play a critical role in ion transport and energy conversion for zinc‐ion batteries (ZIBs). However, the continuous hydrogen‐bond network in highly active H ₂ O molecules facilitates rapid proton transport via the Grotthuss mechanism, exacerbating interfacial side reactions and dendritic growth. Herein, low‐concentration Tetrahydro‐4H‐pyran‐4‐one (THPO) are introduced as a proton blocker to impede proton migration. Equipped with carbonyl and ether groups, THPO disrupts the H ₂ O hydrogen‐bond network by forming strong hydrogen bonds with H ₂ O molecules, thereby impeding proton migration and maintain the stability of the pH value of the electrolyte. Additionally, THPO can act as a capping agent to strongly adsorb on the Zn(100) and Zn(101) crystal planes, directing Zn ² ⁺ deposition toward the Zn(002) plane. This oriented deposition results in a dense and uniform Zn morphology, effectively inhibiting dendritic growth. Benefiting from these synergistic effects, the Zn//Zn symmetric cell achieves a stable cycle life for over 7000 h, while the Zn//Cu asymmetric cell maintains a high Coulombic efficiency of 99.5% after 2000 cycles. Furthermore, the coin full cells and pouch full cells assembled with V ₂ O ₅ cathodes demonstrate promising practical performance.