Achieving Highly Proton‐Resistant Zn–Pb Anode through Low Hydrogen Affinity and Strong Bonding for Long‐Life Electrolytic Zn//MnO₂ Battery

Abstract High‐energy electrolytic Zn//MnO₂ batteries show potential for grid‐scale energy storage, but the severe hydrogen evolution corrosion (HEC) caused by acidic electrolytes results in subdued durability. Here, an all‐around protection strategy is reported for achieving stable Zn metal anodes. First, a proton‐resistant Pb‐containing (Pb and Pb(OH)₂) interface is constructed on a Zn anode (denoted as Zn@Pb), which in situ forms PbSO₄ during H₂SO₄ corrosion and protects the Zn substrate from HEC. Second, to improve the plating/stripping reversibility of Zn@Pb, Pb(CH₃COO)₂ an additive (denoted as Zn@Pb‐Ad) is introduced, which triggers PbSO₄ precipitation and releases trace Pb²⁺ that can dynamically deposit a Pb layer on the Zn plating layer to suppress HEC. The superior HEC resistance stems from the low affinity of PbSO₄ and Pb for H⁺, as well as strong bonding between Pb–Zn or Pb–Pb, which increase the hydrogen evolution reaction overpotential and the H⁺ corrosion energy barrier. Consequently, the Zn@Pb‐Ad//MnO₂ battery runs stably for 630 and 795 h in 0.2 and 0.1 m H₂SO₄ electrolytes, respectively, which are >40 times better than that of bare Zn. The as‐prepared A h‐level battery achieves a one‐month calendar life, opening the door to the next generation of high‐durable grid‐scale Zn batteries.