Designing Zinc Deposition Substrate with Fully Preferred Orientation to Elude the Interfacial Inhomogeneous Dendrite Growth

Abstract

The development of zinc-ion batteries with high energy density remains a great challenge due to the uncontrollable dendrite growth on their zinc metal anodes. Film anodes plated on the substrate have attracted increasing attention to alleviate these dendrite issues. Herein, we first point out that both the random crystal orientation and the low metal affinity of the substrate are important factors of zinc dendrite formation. Accordingly, the (1 0 1) fully preferred tin interface layer with high zinc affinity was fabricated by chemical tin plating on (1 0 0) oriented copper. This tin decorated copper substrate can realize high reversible zinc plating/stripping behavior, and full cell using this zinc plated substrate can be operated for more than 1000 cycles with high capacity retention (85.3%) and low electrochemical impedance. The proposed strategy can be also applied to lithium metal batteries, which demonstrates that the substrate orientation regulation and metal affinity design are the promising approaches to achieve dendrite-free metal anode and overcome the challenges of highly reactive metal anodes.

Discovering the Intrinsic Causes of Dendrite Formation in Zinc Metal Anodes: Lattice Defects and Residual Stress

“…The binding energy of the Zn(1 0 1) crystal surface in the tensile stress state is also higher than that in the compressive stress state (Figure S23). The calculation results show a correlation between the binding energy and the lattice spacing, where the facet with an expanded lattice has a higher binding energy, indicating that zinc is preferentially deposited in areas of lattice expansion rather than in normal and compressed lattice positions [5b] . However, the defects and stresses are not uniformly distributed in commercial zinc anode, which can increase the degree of lattice disorder and thus trigger inhomogeneous zinc deposition.…”

Bulk‐Phase Reconstruction Enables Robust Zinc Metal Anodes for Aqueous Zinc‐Ion Batteries

“…On the surfaces of SR1−Zn−N and C−Zn, zinc is preferentially deposited at the edge of holes on the surface in the plating infancy due to the accumulation of local current density and subsequently evolves into zinc dendrites (Figure S17 and S18) [6b] . Although a relatively smooth surface is obtained on the SR2−Zn−A after stripping, zinc dendrite cannot be suppressed either due to the lack of highly zincophilic surfaces (Figure S19) [17] . Conversely, a smooth and compact plating layer is achieved by the nitrogen‐rich surfaces with high zincophilicity on the post‐stripped BR−Zn (Figure S20).…”

“…[6b] Although a relatively smooth surface is obtained on the SR2À ZnÀ A after stripping, zinc dendrite cannot be suppressed either due to the lack of highly zincophilic surfaces (Figure S19). [17] Conversely, a smooth and compact plating layer is achieved by the nitrogen-rich surfaces with high zincophilicity on the post-stripped BRÀ Zn (Figure S20). The positive effect of nitrogen-rich surface was also verified by the zinc deposition behavior on the fresh surfaces of these zinc foil anodes (Figure S21).…”

A common polar dye additive as corrosion inhibitor and leveling agent for stable aqueous zinc‐ion batteries

“…5 However, side reactions at electrode-electrolyte interface (EEI) can induce electrolyte loss and impedance increase and the uncontrolled and rampant dendrite growth during charge-discharge cycles can potentially result in internal short circuits, severely limiting the commercialization process of AZIBs. 6 Numerous strategies, such as current collector design, 7,8 zinc metal modification, [9][10][11][12] separator optimization, 13,14 and electrolyte engineering, 15,16 can address these above issues. Among them, the introduction of functional additives is an effective method because of its simplicity and scalability.…”

“…Aqueous zinc‐ion batteries (AZIBs) are conspicuous due to high natural abundance, safety and high theoretical capacity (820 mAh g −1 ) 5 . However, side reactions at electrode–electrolyte interface (EEI) can induce electrolyte loss and impedance increase and the uncontrolled and rampant dendrite growth during charge–discharge cycles can potentially result in internal short circuits, severely limiting the commercialization process of AZIBs 6 …”