Understanding H₂ Evolution Electrochemistry to Minimize Solvated Water Impact on Zinc-Anode Performance

H₂ evolution is the reason for poor reversibility and limited cycle stability with Zn-metal anodes, and impedes practical application in aqueous zinc-ion batteries (AZIBs). Here, using a combined gas chromatography experiment and computation, it is demonstrated that H₂ evolution primarily originates from solvated water, rather than free water without interaction with Zn²⁺. Using linear sweep voltammetry (LSV) in salt electrolytes, H₂ evolution is evidenced to occur at a more negative potential than zinc reduction because of the high overpotential against H₂ evolution on Zn metal. The hypothesis is tested and, using a glycine additive to reduce solvated water, it is confirmed that H₂ evolution and “parasitic” side reactions are suppressed on the Zn anode. This electrolyte additive is evidenced to suppress H₂ evolution, reduce corrosion, and give a uniform Zn deposition in Zn|Zn and Zn|Cu cells. It is demonstrated that Zn|PANI (highly conductive polyaniline) full cells exhibit boosted electrochemical performance in 1 M ZnSO₄–3 M glycine electrolyte. It is concluded that this new understanding of electrochemistry of H₂ evolution can be used for design of relatively low-cost and safe AZIBs for practical large-scale energy storage. © 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.