Spatial Confinement Effect of Mineral‐Based Colloid Electrolyte Enables Stable Interface Reaction for Aqueous Zinc–Manganese Batteries

Magnesium aluminosilicate-based colloid (MAS-Colloid) electrolyte holds great capability to simultaneously address the issues of zinc dendrite and manganese dissolution for Zn//α-MnO₂ batteries owing to the spatial confinement effect of MAS on the active H₂O molecules. MAS-Colloid electrolyte guarantees rapid zinc nucleation and reversible zinc deposition behavior for Zn anode, and suppressive manganese dissolution and stable interfacial reaction for α-MnO₂ cathode.

Abstract

The rational design of inorganic colloid electrolytes enables the manipulation of the solvation structure of Zn²⁺ ions and addresses zinc dendrite formation and manganese dissolution in aqueous zinc–manganese batteries. In this study, magnesium aluminosilicate (MAS) powder is used to fabricate a mineral-based colloid electrolyte for Zn//α-MnO₂ batteries. According to theoretical calculations, MAS has a stronger binding energy with Zn²⁺/Mn²⁺ ions than with H₂O molecules, suggesting the possibility of regulating the solvation structure of Zn²⁺/Mn²⁺ ions in a MAS–colloid electrolyte. Based on the experimental results, a high ionic conductivity, wide operating voltage, low activation energy barrier, and stable pH environment is achieved in the MAS–colloid electrolyte. As expected, long-term cyclic stability can be maintained for 3500 h at 0.2 mA cm⁻² in Zn//Zn cells, and high capacities of 255.5 and 239.8 mAh g⁻¹ are retained at 0.2 and 0.5 A g⁻¹ after 100 cycles in Zn//α-MnO₂ batteries, respectively. This performance is attributed to the spatial confinement effect of MAS on the active H₂O molecules, which effectively reshapes the solvation structure of Zn²⁺ ions, guaranteeing reversible zinc deposition, suppressing active manganese dissolution, and ensuring stable interfacial reactions. This work will drive the development of mineral-based electrolytes in zinc-based batteries.