The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based...The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.展开更多
Aqueous zinc-ion batteries(AZIBs) have garnered significant attention as promising candidates for gridscale energy storage.However,the interfacial instability of zinc anodes caused by the hydrogen evolution reaction(H...Aqueous zinc-ion batteries(AZIBs) have garnered significant attention as promising candidates for gridscale energy storage.However,the interfacial instability of zinc anodes caused by the hydrogen evolution reaction(HER) and aqueous electrolyte corrosion severely restricts their practical implementation.This study introduces 2-mercaptothiazoline(MT) as a dynamic electrolyte additive,leveraging its thiolthione tautomerism for interfacial stabilization.Theoretical calculations and experimental investigations reveal that MT can adsorb onto the zinc surface to form a protective layer to suppress corrosion.Simultaneously,the spatial effect of the thiazoline ring prevents excessive molecular aggregation while enabling homogeneous Zn^(2+) electrodeposition.The electronegativity difference between sulfur and nitrogen atoms induces localized polarization,strengthening electronic interactions with the metal surface to accelerate Zn^(2+) reduction kinetics and inhibit side reactions.Consequently,smooth and low-porosity Zn deposits with enhanced interfacial stability are achieved.The optimized Zn//Zn symmetric cells exhibit extraordinary cycling stability exceeding 1800 h at 0.5 mA cm^(-2),0.5 mAh cm^(-2),while sustaining400 h of operation at 28.5 % depth of discharge(DOD).Zn//MnO_(2) full cells incorporating MT additive maintain 122.6 mAh g^(-1) capacity retention after 500 cycles(1 A g^(-1)).This work provides a facile yet effective strategy for stabilizing Zn metal-based batteries through synergistic interface engineering.展开更多
基金Natural Science Foundation of Hunan Province (No.2020JJ4734)High Performance Computing Center of Central South University。
文摘The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.
基金supported by the Natural Science Foundation of Hunan Province (No.2020JJ4734)supported in part by the High Performance Computing Center of Central South University。
文摘Aqueous zinc-ion batteries(AZIBs) have garnered significant attention as promising candidates for gridscale energy storage.However,the interfacial instability of zinc anodes caused by the hydrogen evolution reaction(HER) and aqueous electrolyte corrosion severely restricts their practical implementation.This study introduces 2-mercaptothiazoline(MT) as a dynamic electrolyte additive,leveraging its thiolthione tautomerism for interfacial stabilization.Theoretical calculations and experimental investigations reveal that MT can adsorb onto the zinc surface to form a protective layer to suppress corrosion.Simultaneously,the spatial effect of the thiazoline ring prevents excessive molecular aggregation while enabling homogeneous Zn^(2+) electrodeposition.The electronegativity difference between sulfur and nitrogen atoms induces localized polarization,strengthening electronic interactions with the metal surface to accelerate Zn^(2+) reduction kinetics and inhibit side reactions.Consequently,smooth and low-porosity Zn deposits with enhanced interfacial stability are achieved.The optimized Zn//Zn symmetric cells exhibit extraordinary cycling stability exceeding 1800 h at 0.5 mA cm^(-2),0.5 mAh cm^(-2),while sustaining400 h of operation at 28.5 % depth of discharge(DOD).Zn//MnO_(2) full cells incorporating MT additive maintain 122.6 mAh g^(-1) capacity retention after 500 cycles(1 A g^(-1)).This work provides a facile yet effective strategy for stabilizing Zn metal-based batteries through synergistic interface engineering.
