Anion Texturing Towards Dendrite‐Free Zn Anode for Aqueous Rechargeable Batteries

Abstract

The reversibility of metal anode is a fundamental challenge to the lifetime of rechargeable batteries. Though being widely employed in aqueous energy storage systems, metallic zinc suffers from dendrite formation that severely hinders its applications. Here we report texturing Zn as an effective way to address the issue of zinc dendrite. An in‐plane oriented Zn texture with preferentially exposed (002) basal plane is demonstrated via a sulfonate anion‐induced electrodeposition, noting no solid report on (002) textured Zn till now. Anion‐induced reconstruction of zinc coordination is revealed to be responsible for the texture formation. Benchmarking against its (101) textured‐counterpart by the conventional sulphate‐based electrolyte, the Zn (002) texture enables highly reversible stripping/plating at a high current density of 10 mA cm−2, showing its dendrite‐free characteristics. The Zn (002) texture‐based aqueous zinc battery exhibits excellent cycling stability. The developed anion texturing approach provides a pathway towards exploring zinc chemistry and prospering aqueous rechargeable batteries.

Textured Electrodes: Manipulating Built‐In Crystallographic Heterogeneity of Metal Electrodes via Severe Plastic Deformation

“…Very recently, a small number of works revealed that the crystallography of metal deposits plays a critical, but previously underexplored role in plating/stripping processes. [14][15][16] These studies showed that the crystallographic features of a metal deposit formed at the interface can serve as a sensitive indicator of the electrodeposition quality, including the geometry of the crystallite building blocks and the orientational order parameter with respect to the electrode surface. [9] A universal rule, independently established in different metal systems, e.g., Zn [14,17] and Li, [8,18] is that stable plating/stripping can be achieved when the deposits exhibit a strong crystallographic texture (e.g., as produced by aligning the close-packed crystal plane with the substrate).…”

A Lewis acidity adjustable organic ammonium cation derived robust protecting shield for stable aqueous zinc-ion batteries by inhibiting the tip effect

“…In previous studies, the larger the absolute value of E ads of the group is, the more likely it is to form a positive shielding layer on the Zn surface, and therefore the easier it is to optimize the performance of the battery. [29][30][31] Interestingly, the tetrabutylammonium cation (TBA + ) has the highest absolute value of E ads (À4.424 eV) and therefore it is most easily adsorbed on the zinc surface, but the experimental results demonstrated that its improvement effect on battery performance is not the best. Therefore, further study of differential charge density analyses is used to explain the nature of the phenomenon (Fig.…”

Understanding and Performance of the Zinc Anode Cycling in Aqueous Zinc‐Ion Batteries and a Roadmap for the Future

“…Subsequently, this stabilization leads to sufficient coverage of Zn adions on the surface of the substrate, which facilitates the formation of hexagonal nuclei (Figure 14a). As a result, the hexagonally arranged nuclei further aggregate and parallelly grow along the (002) facet till touching the neighboring nuclei to form a continuous film (Figure 14b) [96] . In another work, Cong et al.…”

“…In this context, some electrolytes have been explored that can endow selective deposition of textured Zn to enable dendrite free operation. For instance, the zinc trifluoromethanesulfonate [Zn(OTf) 2 ] can alter the zinc coordination in the salt‐in‐water electrolyte and further prompt the formation of Zn (002) texture via the strong OTf anion‐Zn 2+ interaction [96] . The proposed mechanism is that at the onset of electrodeposition, the OTf − anions, propelled by the enormous adsorption energy of −13.9 eV with the Cu substrate, promote the stabilization of adsorbed Zn ions (or adions) on the flat surface sites of the substrate.…”

“…For instance, the zinc trifluoromethanesulfonate [Zn(OTf) 2 ] can alter the zinc coordination in the salt-in-water electrolyte and further prompt the formation of Zn (002) texture via the strong OTf anion-Zn 2 + interaction. [96] The proposed mechanism is that at the onset of electrodeposition, the OTf À anions, propelled by the enormous adsorption energy of À 13.9 eV with the Cu substrate, promote the stabilization of adsorbed Zn ions (or adions) on the flat surface sites of the substrate. Subsequently, this stabilization leads to sufficient coverage of Zn adions on the surface of the substrate, which facilitates the formation of hexagonal nuclei (Figure 14a).…”