Recent years have witnessed the renaissance of aqueous Zn-ion batteries (AZIBs). Nevertheless, current development of high-performance AZIBs is confronted by rapid capacity decay and irreversible cycling of Zn anodes, whose...

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+, thus inhibiting hydrogen evolution and side reactions. The self‐assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm−2/1.0 mAh cm−2.

Constructing a conductive carbon-based artificial interphase layer (AIL) to inhibit dendritic formation and side reaction plays a pivotal role in achieving longevous Zn anodes. Distinct from the previously reported carbonaceous overlayers with singular dopants and thick foreign coatings, a new type of N/O co-doped carbon skin with ultrathin feature (i.e., 20 nm thickness) is developed via the direct chemical vapor deposition growth over Zn foil. Throughout fine-tuning the growth conditions, mosaic nanocrystalline graphene can be obtained, which is proven crucial to enable the orientational deposition along Zn (002), thereby inducing a planar Zn texture. Moreover, the abundant heteroatoms help reduce the solvation energy and accelerate the reaction kinetics. As a result, dendrite growth, hydrogen evolution, and side reactions are concurrently mitigated. Symmetric cell harvests durable electrochemical cycling of 3040 h at 1.0 mA cm −2 /1.0 mAh cm −2 and 136 h at 30.0 mA cm −2 /30.0 mAh cm −2 . Assembled full battery further realizes elongated lifespans under stringent conditions of fast charging, bending operation, and low N/P ratio. This strategy opens up a new avenue for the in situ construction of conductive AIL toward pragmatic Zn anode.

Zn foil pretreatment is a direct route to alleviating Zn anode instability and maintaining high energy performance in Zn metal batteries. Unfortunately, prevailing methods for achieving an ideal Zn surface texture do not enable durable operation under a large depth of discharge, thus impairing the Zn utilization ratio. Zn etching is a more feasible way to control the surface texture, but this approach remains relatively unexplored. In this study, a general strategy is reported for Zn foil engraving in aprotic media to realize efficient anode pretreatment in terms of stability. These tests are performed using high-valence metal ions (especially Mo 5+ ) in an aprotic environment as the key etchant to render a homogenously-distributed, 3D porous architecture on the Zn foil surface. Comprehensive experimental results and theoretical simulations revealed enhanced Zn nucleation and growth. This specially designed electrode exhibited a long lifespan with a large depth of discharge of 88% in symmetric cells. When assembled with a Zn x V 2 O 5 cathode, the constructed cell demonstrated nearly full capacity retention even under stringent conditions (e.g., an N/P capacity ratio of 5.5). This study demonstrates the potential of a Zn etching pretreatment to address the prototypical instability issues of Zn anodes.

Electroepitaxy is recognized as an effective approach to prepare metal electrodes with nearly complete reversibility. Nevertheless, large‐scale manipulation is still not attainable owing to complicated interfacial chemistry. Here, the feasibility of extending Zn electroepitaxy toward the bulk phase over a mass‐produced mono‐oriented Cu(111) foil is demonstrated. Interfacial Cu–Zn alloy and turbulent electroosmosis are circumvented by adopting a potentiostatic electrodeposition protocol. The as‐prepared Zn single‐crystalline anode enables stable cycling of symmetric cells at a stringent current density of 50.0 mA cm−2. The assembled full cell further sustaines a capacity retention of 95.7% at 5.0 A g−1 for 1500 cycles, accompanied by a controllably low N/P ratio of 7.5. In addition to Zn, Ni electroepitaxy can be realized by using the same approach. This study may inspire rational exploration of the design of high‐end metal electrodes.

The unsatisfactory cycling stability of Zn anode stemming from dendritic growth and side reactions has slowed the rapid development of aqueous Zn-ion batteries (AZIBs). Constructing a three-dimensional (3D) artificial interphase layer is an appealing solution since it could dictate Zn deposition at the interface. Here, the in situ growth of a Cu-based metal–organic framework (Cu-MOF) over commercial Zn foil followed by subsequent selenization endows selenized Cu-MOF (SCM) with a stabilized Zn anode. The 3D SCM coating could homogenize the electric field and function as a reservoir to tolerate the deposited Zn. As a result, both rampant dendritic propagation and the notorious side reactions are concurrently inhibited. The SCM@Zn symmetric cell displays an elongated cyclic life for over 500 h at 2.0 mA cm–2. The assembled AZIB full cell readily realizes high electrochemical reversibility under different current densities. Our investigation offers insights into the design of a protective layer for high-performance Zn anodes.

Constructing a conductive carbon-based artificial interphase layer (AIL) to inhibit dendritic formation and side reaction plays a pivotal role in achieving longevous Zn anodes. Distinct from the previously reported carbonaceous overlayers with sigular dopants and thick foreign coatings, a new type of N/O co-doped carbon skin with ultrathin feature (i.e., 20 nm thickness) is developed via the direct chemical vapor deposition growth over Zn foil. Throughout fine-tuning the growth conditions, mosaic nanocrystalline graphene could be obtained, which is proven crucial to enable the orientational deposition along Zn (002), thereby inducing a planar Zn texture. Moreover, the abundant heteroatoms help reduce the solvation energy and accelerate the reaction kinetics. As a result, dendrite growth, hydrogen evolution and side reactions are concurrently mitigated. Symmetric cell harvests durable electrochemical cycling of 3040 h at 1.0 mA cm− 2/1.0 mAh cm− 2 and 136 h at 30.0 mA cm− 2/30.0 mAh cm− 2. Assembled full battery further realizes elongated lifespans under stringent conditions of fast charging, bending operation and low N/P ratio. This strategy opens up a new avenue for the in-situ construction of conductive AIL toward pragmatic Zn anode.

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+, thus inhibiting hydrogen evolution and side reactions. The self‐assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm−2/1.0 mAh cm−2.