Coupling of Donor–Acceptor of Hydrogen Bonds Manipulated Electrolyte Structure Enables Hydrogen Evolution‐Free and Durable Zn Metal Batteries

Abstract The undesirable hydrogen evolution reaction (HER) primarily contributes to the instability of Zn anode, which exacerbates Zn corrosion and dendrite growth and impedes the application of Zn metal battery in large‐scale energy storage. Although engineering functional aqueous electrolyte prominently controls HER, it hardly eradicates the occurrence of HER from the source. Herein, this research utilizes the coupling of donor–acceptor of hydrogen bonds (H‐bonds) to manipulate electrolyte structure and design a novel methanol (MeOH)‐based anhydrous organic electrolyte with propylene carbonate (PC) as co‐solvent, fundamentally eliminating HER, accompanied by suppressed corrosion and dendrite growth. The PC molecules as acceptor strengthen the H‐bonds networks between MeOH donor molecules and weaken the interaction of cations and anions, enhancing the stability of electrolyte and reducing the anion‐involved by‐products formation. Meanwhile, the preferential adsorbed PC molecules on the anode surface form favorable organic component‐dominated solid electrolyte interface layer, inducing uniform Zn deposition along (002) orientation. Consequently, Zn anode in the anhydrous organic electrolyte exhibits excellent cycling stability and high reversibility. The assembled cells also harvest a satisfactory low‐temperature tolerance. More importantly, the corresponding Zn||PANI full cell and pouch cell behave an impressive capacity retention of 92.4% and 91.1% after 3200 and 1400 cycles, respectively.