Bifunctional Dynamic Adaptive Interphase Reconfiguration for Zinc Deposition Modulation and Side Reaction Suppression in Aqueous Zinc Ion Batteries

Abstract

Dendrite growth and electrode/electrolyte interface side reactions in aqueous zinc-ion batteries (AZIBs) not only impair the battery lifetime but also pose serious safety concerns for the battery system, hindering its application in large-scale energy storage systems. Herein, by introducing positively charged chlorinated graphene quantum dot (Cl-GQD) additives into the electrolyte, a bifunctional dynamic adaptive interphase is proposed to achieve Zn deposition regulation and side reaction suppression in AZIBs. During the charging process, the positively charged Cl-GQDs are adsorbed onto the Zn surface, acting as an electrostatic shield layer that facilitates smooth Zn deposition. In addition, the relative hydrophobic properties of chlorinated groups also build a hydrophobic protective interface for the Zn anode, mitigating the corrosion of the Zn anode by water molecules. More importantly, the Cl-GQDs are not consumed throughout the cell operation and exhibit a dynamic reconfiguration behavior, which ensures the stability and sustainability of this dynamic adaptive interphase. Consequently, the cells mediated by the dynamic adaptive interphase enable dendrite-free Zn plating/stripping for more than 2000 h. Particularly, even at 45.5% depth of discharge, the modified Zn//LiMn 2 O 4 hybrid cells still retain 86% capacity retention after 100 cycles, confirming the feasibility of this simple approach for application with limited Zn sources.

Engineering functionalization and properties of graphene quantum dots (GQDs) with controllable synthesis for energy and display applications

“…307 In a recent paper, Wang et al reduced the surface growth and interfacial side reactions of AZIB by introducing Cl-GQDs into the electrolyte. 308 The key insight of their study is the electrostatic adsorption of Cl-GQDs, allowing control over the charge state and relative hydrophobicity of the SEI, yielding effects similar to those depicted in Fig. 11.…”

Toward Simultaneous Dense Zinc Deposition and Broken Side‐Reaction Loops in the Zn//V2O5 System

“…[2] Presently, the most promising AZIBs comprise Zn//manganese-based oxides (MnO 2 , Mn 2 O 3 , Mn 3 O 4 ), [3] Zn//vanadium-based oxides (V 2 O 5 , VO 2 , V 2 O 3 ) [4] and Zn//Prussian blue analogs (Zn 3 [Fe-(CN) 6 ] 2 ). [5] However, various hurdles, such as unstable electrodes, [6] corrosive electrolytes, [7] and unsuitable battery systems, [8] significantly impede their development. In the case of AZIBs coupled with Zn anodes and V 2 O 5 cathodes, which have been widely investigated due to the high energy density and cost-effectiveness, [9] they not only face common problems such as dissolution and collapse of cathode materials, [10] Zn anode dendrite growth, [11] hydrogen evolution and corrosion passivation, [12] but are also limited by some secondary issues.…”

Artificial Hydrophilic Organic and Dendrite-Suppressed Inorganic Hybrid Solid Electrolyte Interface Layer for Highly Stable Zinc Anodes

“…Lithium-ion batteries (LIBs) are prevalent in green energy storage devices, such as portable devices and electric vehicles, due to their high energy density and good rechargeability. , However, lithium ore resources are scarce, and the inherent price is high. − Lithium-ion batteries use toxic and flammable organic electrolytes, which have potential safety hazards and are easy to cause environmental pollution, which seriously hinders their further application in the field of energy storage. − It is urgent to develop new batteries to replace lithium-ion batteries. − Aqueous zinc -ion batteries (AZIBs) are considered to be a reliable alternative to LIBs. It shows a high safety characteristic due to their use of aqueous electrolytes. − However, aqueous zinc-ion batteries have poor energy density and cycle life due to side reactions, such as dendrite growth, hydrogen evolution reaction (HER), and corrosion, as well as low zinc utilization (often referred to as depth of discharge, DOD) and undesired Coulombic efficiency (Scheme a). − Addressing these issues, particularly improving the reversibility of zinc metal, is crucial for enhancing the performance of aqueous zinc metal batteries. − …”