Labile Coordination Interphase for Regulating Lean Ion Dynamics in Reversible Zn Batteries

Abstract

The rechargeable Zn battery technology is plagued with limited reversibility on the anode. The issue is particularly exacerbated when using lean electrolytes, which compromises the economic advantages of zinc batteries for large‐scale energy storage. In this paper, we report the development of a zinc‐coordinated interphase that prevents chemical corrosion and provides protection for zinc anodes. The selective binding of Zn2+ ions towards histidine and carboxylate ligands forms a coordination environment that offers high Zn2+ affinity and fast Zn2+ diffusion owing to its thermodynamic stability and kinetic lability. Both experiments and calculations suggest that the interphase mitigates side reactions and regulates the dendrite‐free electrodeposition. Implementing this labile coordination interphase yields enhanced cycling at a high current density of 20 mA cm−2 with high reversibility of dendrite‐free zinc plating/stripping for more than 200 hours. The reversibility was demonstrated in a Zn||LiMn2O4 cell, which shows an energy density of 74.7 mWh g−1 and a Coulombic efficiency of 99.7% after 500 cycles. In addition, we demonstrate a lean‐electrolyte full cell utilizing electrolyte of only 10 μL mAh−1. This cell operates for an extended cycling life of 100 cycles, five times longer than the pristine Zn anodes. This provides an energy density that is significantly higher than that of commercial aqueous batteries. This work demonstrates a proof‐of‐concept design for utilizing labile coordination interphases on Zn anodes, offering an approach for low‐electrolyte usage and the manufacture of high‐energy‐density batteries.This article is protected by copyright. All rights reserved

Bio‐Inspired Trace Hydroxyl‐Rich Electrolyte Additives for High‐Rate and Stable Zn‐Ion Batteries at Low Temperatures

“…However, due to the additional reaction between Cl − ions and active H 2 O molecules in the Zn 2+ solvation layer (e.g., [Zn(H 2 O) 6 ] 2+ , [Zn(H 2 O) 2 Cl 4 ] 2− ), the Zn anode experiences exaggeratedly corrosion and hydrogen evolution reaction (HER) issues, [29–31] thus stable cycling performance can only be achieved at low current densities (e.g., 0.2 mA cm −2 ). In addition, the kinetics of Zn 2+ de‐solvation tend to slow down, which results in poor rate capability with uneven Zn nucleation and deposition [32–35] . Especially at high current density, Zn electrodes face the risk of local de‐solvation difficulty and serious corrosion from the electrolyte, resulting in dendrite growth and short circuit after long‐term cycling [36–40] .…”

“…In addition, the kinetics of Zn 2 + de-solvation tend to slow down, which results in poor rate capability with uneven Zn nucleation and deposition. [32][33][34][35] Especially at high current density, Zn electrodes face the risk of local de-solvation difficulty and serious corrosion from the electrolyte, resulting in dendrite growth and short circuit after long-term cycling. [36][37][38][39][40] Therefore, it will be of great interest to develop new strategies for electrolytes that can simultaneously solve corrosion and kinetics problems at low temperatures, ultimately achieving low-temperature Zn anodes with superior stability at high rate (� 5 mA cm À 2 ).Four-season plants, such as cedar, maintain their vivid appearance even at winter time, which could provide a meaningful reference for low-temperature ZIBs.…”

Interfacial Engineering of Zn Metal via a Localized Conjugated Layer for Highly Reversible Aqueous Zinc Ion Battery

“…designed a heteroanionic zinc ion conductor (Zn y O 1‐x F x ) interphase with fast Zn 2+ transference kinetics. Wang et al [6c] . prepared a Zn‐coordinated interphase (H‐ZnCND) to regulate Zn deposition and stabilize Zn anodes.…”

Recent Developments of Carbon Dots for Advanced Zinc‐Based Batteries: A Review

“…In addition, the inertness, nontoxicity, and processibility of Zn metal ensure Zn‐based batteries have the advantages of simple assembly, environmental friendliness, and excellent cycle capability. [ 6–8 ] More importantly, different from conventional LIBs using organic electrolytes, Zn‐based batteries are expected to acquire higher power density, better security, and lower production costs because water as the solvent possesses the advantages of higher ionic conductivity, nonflammability, and ease of extract compared with organic solvents. Yet, the genuine application of Zn‐based batteries still confronts many troubles that are mainly correlated with the Zn anode, such as inevitable dendrite growth, tough parasitic reactions, and Zn corrosion.…”