Operando pH Measurements Decipher H⁺/Zn²⁺ Intercalation Chemistry in High-Performance Aqueous Zn/δ‑V₂O₅ Batteries

Vanadium oxides have been recognized to be among the most promising positive electrode materials for aqueous zinc metal batteries (AZMBs). However, their underlying intercalation mechanisms are still vigorously debated. To shed light on the intercalation mechanisms, high-performance δ-V₂O₅ is investigated as a model compound. Its structural and electrochemical behaviors in the designed cells with three different electrolytes, i.e., 3 m Zn­(CF₃SO₃)₂/water, 0.01 M H₂SO₄/water, and 1 M Zn­(CF₃SO₃)₂/acetonitrile, demonstrate that the conventional structural and elemental characterization methods cannot adequately clarify the separate roles of H⁺ and Zn²⁺ intercalations in the Zn­(CF₃SO₃)₂/water electrolyte. Thus, an operando pH determination method is developed and used toward Zn/δ-V₂O₅ AZMBs. This method indicates the intercalation of both H⁺ and Zn²⁺ into δ-V₂O₅ and uncovers an unusual H⁺/Zn²⁺-exchange intercalation–deintercalation mechanism. Density functional theory calculations further reveal that the H⁺/Zn²⁺ intercalation chemistry is a consequence of the variation of the electrochemical potential of Zn²⁺ and H⁺ during the electrochemical intercalation/release.