Cathode–Electrolyte Interface Modification by Binder Engineering for High‐Performance Aqueous Zinc‐Ion Batteries

A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO^- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn²⁺ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn²⁺ at the CEI, where the Zn-Birnessite MnO₂ battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.