Cationic Surfactant-Type Electrolyte Additive Enables Three-Dimensional Dendrite-Free Zinc Anode for Stable Zinc-Ion Batteries

Abstract

Zn metal has been considered as a promising anode material for rechargeable aqueous metal-ion batteries. However, the propensity of dendrite growth during plating restricts its practical applications. Herein we propose an effective, low-cost, and nontoxic electrolyte additive, tetrabutylammonium sulfate (TBA2SO4), as the first example of a cationic surfactant-type electrolyte additive in Zn-ion batteries, which can induce the uniform Zn deposition in both electrode preparation and the battery charge/discharge process. Electrochemical characterizations, in situ optical microscopy observation, along with density functional theory (DFT) calculations reveal the unique zincophobic repulsion mechanism, which results in the minimum addition amount of 0.029 g L–1 compared with other reported additives (at least 1g L–1), demonstrating the great potential for practical application. Excellent cycling performance with dendrite-free morphology at different current densities and discharge depths is achieved for both the symmetric cell and the full cell (coupled to α-MnO2) using the as-prepared 3D Zn anode and the proposed additives.

Simultaneous Regulation on Solvation Shell and Electrode Interface for Dendrite‐Free Zn Ion Batteries Achieved by a Low‐Cost Glucose Additive

“…As shown in Figures 4 c and S17, the Zn//Zn symmetric coin cell using ZnSO 4 ‐glucose electrolyte can stably cycle for over 2000 h at 1 mA cm −2 with 1 mAh cm −2 and 740 h at 2 mA cm −2 with 2 mAh cm −2 , while those using pure ZnSO 4 electrolyte are short‐circuited after 300 and 200 h of cycling under the same conditions. More attractively, even employing a high current of 5 mA cm −2 and a high capacity of 5 mAh cm −2 , this novel electrolyte system still supports stably reversible Zn plating/stripping for around 270 h (Figure 4 d), which is much superior to that using pure ZnSO 4 (around 20 h) and better than most of previous work (Table S1) [11, 13, 14, 21, 23–26, 36, 44, 45] …”

“Water‐in‐Deep Eutectic Solvent” Electrolytes for High‐Performance Aqueous Zn‐Ion Batteries

“…[ 32 ] In the Zn deposition process, the Zn 2+ absorbed on the collector surface would diffuse and aggregate into large nucleation sites to reduce the surface energy of the system (Figure 3e). [ 33–35 ] Traditional electrostatic shielding mechanism is the most commonly used method to induce homogeneous Zn deposition. [ 36–38 ] The surface of the protruding Zn dendrite would be covered by the conventional additives, such as diethyl ether, which has little effect on the Zn 2+ solvation structure but can form a thin layer of protection shell.…”

Heterometallic Seed‐Mediated Zinc Deposition on Inkjet Printed Silver Nanoparticles Toward Foldable and Heat‐Resistant Zinc Batteries

“…Impressively, such long cycle life is superior to those of many previously reported Zn anodes at the same current density (Figure 5e). [ 31,36,39,48–52 ]…”