Colloid Electrolyte with Weakly Solvated Structure and Optimized Electrode/Electrolyte Interface for Zinc Metal Batteries

Aqueous zinc batteries are considered as a viable candidate for cost-effective and environmentally sustainable energy storage technology but are severely hampered by the notorious dendrite growth and parasitic reactions at the zinc anode side. Herein, we propose a bifunctional colloidal electrolyte design that utilizes upconversion nanocrystals, i.e., NaErF₄@NaYF₄, as a solid additive to provide the sustained release of functional metal and fluoride ions, which can effectively improve the reversibility of the Zn anode to inhibit dendrite growth and hydrogen evolution through forming an electrostatic shielding layer and in situ constructing a ZnF₂-enriched protective interface. Experimental characterization and molecular dynamics simulation jointly confirm that the NaErF₄@NaYF₄ additive could modify the Zn²⁺ solvation environment in the vicinity of the NaErF₄@NaYF₄ surface via the strong electrostatic coupling with Zn²⁺ ions. As a consequence, the modified electrolyte enables stable zinc plating/stripping over 2100 h at a current density of 3 mA cm^-2 and a capacity of 1 mAh cm^-2 in symmetric cells. The assembled Zn||MnO₂ full cells with a modified electrolyte can operate stably for 1600 cycles at 2 A g^-1. This work thereby has great potential for the exploration of multifunctional electrolyte additives toward long-lasting aqueous Zn metal batteries.