An Artificial Interphase Engineering Simultaneously Suppressing Hydrogen Evolution Reaction and Controlling Zinc Dendrite Growth to Achieve Stable Zinc Metal Anodes

Abstract

Zinc metal anode, the most promising candidate material for rechargeable aqueous zinc‐ion batteries, has attracted considerable attention due to its abundant resources and low cost. However, hydrogen evolution reaction and uncontrollable zinc dendrite growth on zinc metal anode are the essential issues that strictly limit their practical application. Here, a modified Zn with a titanium nitride (TiN) protective layer (TiN@Zn) using a simple solvent casting approach is developed, which can simultaneously suppress the hydrogen evolution reaction and control the zinc dendrite growth when acting like a protective layer on the Zn anode. In situ differential electrochemical mass spectrometry approach shows that the TiN coating layer can effectively suppress the hydrogen evolution. Additionally, the TiN can offer large Zn nucleation sites, narrowing the Zn nucleation energy barrier, leading to a uniform Zn deposition. Thus, in symmetric cells, the TiN@Zn electrode presents a stable Zn plating/striping (600 h at 1 mA cm−2) and lower potential hysteresis (38 mV), resulting in an improved electrochemical performance for TiN@Zn||MnO2 full cell.

Stabilizing Zn Anodes with Interfacial Engineering for Aqueous Zinc‐ion Batteries

“…Differential electrochem-ical mass spectrometry (DEMS) is a valid technique for in-situ detection of hydrogen evolution to analyze the electrolyte compatibility with Zn. [113] In contract with the bare Zn, the H 2 signal was barely monitored in the case of the ionic liquid skinny gels modified Zn (ILG-Zn), alleviating the HER (Figure 10i). [114] Apart from the above-mentioned in-situ characterizations, other in-situ techniques (i. e., in-situ XRD, in-situ Raman spectroscopy, in-situ FTIR, in-situ AFM) can also be employed as assisted methods to monitor changes of the Zn anodes.…”

“…During the Zn plating process, hydrogen evolution and Zn deposition are a competitive reaction. Differential electrochemical mass spectrometry (DEMS) is a valid technique for in‐situ detection of hydrogen evolution to analyze the electrolyte compatibility with Zn [113] . In contract with the bare Zn, the H 2 signal was barely monitored in the case of the ionic liquid skinny gels modified Zn (ILG‐Zn), alleviating the HER (Figure 10i).…”

Recent Progress in High‐voltage Aqueous Zinc‐based Hybrid Redox Flow Batteries

“…The zinc anode of the ZHFBs has plating and stripping reaction, causing zinc dendritic growth during the charging process. [96][97][98][99] In particular, the zinc dendritic growth in alkaline media hindered the practical application of ESSs. [100] The zincate ions in the alkaline media are plated on the carbon felt or zinc metal plates and tend to grow into dendrites.…”

“…In addition, the dead zinc metal during the discharge process could be removed from the electrode and accumulated in the porous electrode or membrane, degrading the cycle performance. [98,99,101] Recently, many studies have been widely studied to suppress the problem of the zinc dendritic growth in the ZHFBs, such as carbon electrode surface modification through carbonization, sputtering, and membrane modification. [101][102][103][104][105][106][107] Lee et al prevented aggregative zinc growth by using dangling bonds induced by forming a carbon defect layer on the carbon electrode surface.…”

A zincophilic ion-conductive layer with the desolvation effect and oriented deposition behavior achieving superior reversibility of Zn metal anodes

“…The electron-conductive layers are usually designed to achieve suppression of dendrite growth and low polarization voltages, such as carbon nanotubes (CNTs), 21 Cu@Zn, 22 TCNQ@Zn, 23 and TiN. 24 The CNT layer homogenizes the electric field on the electrode surface to obtain dendrite-free Zn deposition. 21 The TCNQ@Zn anode achieves uniform Zn deposition with more Zn (002) due to the lower migration barrier of Zn (002) than Zn (101).…”