Hierarchical Confinement Effect with Zincophilic and Spatial Traps Stabilized Zn-Based Aqueous Battery

Abstract

Zn-based aqueous batteries (ZABs) have been regarded as promising candidates for safe and large-scale energy storage in the "post-Li" era. However, kinetics and stability problems of Zn capture cannot be concomitantly regulated, especially at high rates and loadings. Herein, a hierarchical confinement strategy is proposed to design zincophilic and spatial traps through a host of porous Co-embedded carbon cages (denoted as CoCC). The zincophilic Co sites act as preferred nucleation sites with low nucleation barriers (within 0.5 mA h cm −2 ), and the carbon cage can further spatially confine Zn deposition (within 5.0 mA h cm −2 ). Theoretical simulations and in situ/ ex situ structural observations reveal the hierarchical spatial confinement by the elaborated all-in-one network (within 12 mA h cm −2 ). Consequently, the elaborate strategy enables a dendrite-free behavior with excellent kinetics (low overpotential of ca. 65 mV at a high rate of 20 mA cm −2 ) and stable cycle life (over 800 cycles), pushing forward the next-generation high-performance ZABs.

Methods for Rational Design of Advanced Zn‐Based Batteries

“…Introducing zincophilic sites into carbon is an effective way to solve this issues because zincophilicity play an important role in the initial nucleation and subsequent Zn growth. [ 113 ] For example, Li et al. reported a Sn‐modified 3D carbon felt host for Zn anode.…”

“…Introducing zincophilic sites into carbon is an effective way to solve this issues because zincophilicity play an important role in the initial nucleation and subsequent Zn growth. [113] For example, Li et al reported a Sn-modified 3D carbon felt host for Zn anode. [111] Sn modification can provide the following advantages: i) the stronger electronic interaction of Sn making the Sn possesses more robust sites for Zn deposition; ii) the Sn component can effectively suppress the hydrogen evolution reaction; and iii) Sn endows the carbon with lower Zn deposition overpotential, demonstrating that the Sn could provide more nucleation sites for Zn deposition, which are beneficial for the uniform deposition of Zn.…”

Controlling Horizontal Growth of Zinc Platelet by OP‐10 Additive for Dendrite‐Free Aqueous Zinc‐Ion Batteries

“…[11,19,20] For instance, Li et al designed zincophilic and spatial traps through a host of porous Co-embedded carbon cages, which allows dendrite-free conduct with outstanding kinetics. [21] Zhang et al designed a composite gel electrolyte (TA-SA) from a highly-confined tannic acid (TA) modified sodium alginate (SA), it efficiently suppresses Zn side reactions and dendrite growth. [22] Among them, the optimization of electrolytes is an effective and simple strategy, which includes using electrolyte additives and, selecting the less-water and anhydrous electrolytes with high salinity, gel, and others.…”

“…[22] Among them, the optimization of electrolytes is an effective and simple strategy, which includes using electrolyte additives and, selecting the less-water and anhydrous electrolytes with high salinity, gel, and others. [21][22][23][24][25][26][27] Although the lesswater and anhydrous electrolytes reduce the side reactions caused by free water, their high cost and ionic conductivity lose the advantages of the aqueous electrolytes themselves. By contrast, the electrolyte additives with the unique merit of "small dose and high efficiency", can significantly improve the battery performance without increasing the production cost and production difficulty.…”

“…For instance, Li et al. designed zincophilic and spatial traps through a host of porous Co‐embedded carbon cages, which allows dendrite‐free conduct with outstanding kinetics [21] . Zhang et al.…”