Aqueous zinc-ion batteries have rapidly developed recently as promising energy storage devices in large-scale energy storage systems owing to their low cost and high safety. Research on suppressing zinc dendrite growth has meanwhile attracted widespread attention to improve the lifespan and reversibility of batteries. Herein, design methods for dendrite-free zinc anodes and their internal mechanisms are reviewed from the perspective of optimizing the host-zinc interface and the zinc-electrolyte interface. Furthermore, a design strategy is proposed to homogenize zinc deposition by regulating the interfacial electric field and ion distribution during zinc nucleation and growth. This Minireview can offer potential directions for the rational design of dendrite-free zinc anodes employed in aqueous zinc-ion batteries.

Interfacial design of dendrite‐free zinc anodes for aqueous zinc‐ion batteries

Aqueous Zn batteries that provide a synergistic integration of absolute safety and high energy density have been considered as highly promising energy-storage systems for powering electronics. Despite the rapid progress made in developing high-performance cathodes and electrolytes, the underestimated but non-negligible dendrites of Zn anode have been observed to shorten battery lifespan. Herein, this dendrite issue in Zn anodes, with regard to fundamentals, protection strategies, characterization techniques, and theoretical simulations, is systematically discussed. An overall comparison between the Zn dendrite and its Li and Al counterparts, to highlight their differences in both origin and topology, is given. Subsequently, in-depth clarifications of the specific influence factors of Zn dendrites, including the accumulation effect and the cathode loading mass (a distinct factor for laboratory studies and practical applications) are presented. Recent advances in Zn dendrite protection are then comprehensively summarized and categorized to generate an overview of respective superiorities and limitations of various strategies. Accordingly, theoretical computations and advanced characterization approaches are introduced as mechanism guidelines and measurement criteria for dendrite suppression, respectively. The concluding section emphasizes future challenges in addressing the Zn dendrite issue and potential approaches to further promoting the lifespan of Zn batteries.

Dendrites in Zn-Based Batteries.

Rechargeable aqueous metal-ion batteries are very promising as alternative energy storage devices during the post-lithium-ion era because of their green and safe inherent features. Among the different aqueous metal-ion batteries, aqueous zinc-ion batteries (ZIBs) have recently been studied extensively due to their unique and outstanding benefits that hold promise for large-scale power storage systems. However, zinc anode problems in ZIBs, such as zinc dendrites and side reactions, severely shorten the ZIB's cycle lifetime, thus restricting their practical application. Here, we sum up in detail the recent progress on general strategies to suppress zinc dendrites and zinc anode side reactions based on advanced materials and structure design, including the modification of the planar zinc electrode surface layer, internal structural optimization of the zinc bulk electrode, modification of the electrolyte and construction of the multifunctional separator. The various functional materials, structures and battery efficiencies are discussed. Finally, the challenges for ZIBs are identified in the production of functional zinc anodes.

Challenges in the material and structural design of zinc anode towards high-performance aqueous zinc-ion batteries

A Sieve-Functional and Uniform-Porous Kaolin Layer toward Stable Zinc Metal Anode

Metallic zinc is a promising anode candidate of aqueous zinc-ion batteries owing to its high theoretical capacity and low redox potential. However, Zn anodes usually suffer from dendrite and side reactions, which will degrade their cycle stability and reversibility. Herein, we developed an in situ spontaneously reducing/assembling strategy to assemble a ultrathin and uniform MXene layer on the surface of Zn anodes. The MXene layer endows the Zn anode with a lower Zn nucleation energy barrier and a more uniformly distributed electric field through the favorable charge redistribution effect in comparison with pure Zn. Therefore, MXene-integrated Zn anode exhibits obviously low voltage hysteresis and excellent cycling stability with dendrite-free behaviors, ensuring the high capacity retention and low polarization potential in zinc-ion batteries.

Direct Self‐Assembly of MXene on Zn Anodes for Dendrite‐Free Aqueous Zinc‐Ion Batteries

The zinc metal is recognized as one of the most promising anodes for Zn-based batteries in an energy-storage system. However, the deposition and transfer of bivalent Zn2+ into the host structure suffer from sluggish kinetics accompanying the side-reactions at the interface. Herein, we report a new class of Zn anodes modified by a three-dimensional (3D) nanoporous ZnO architecture coating on a Zn plate (designated as Zn@ZnO-3D) prepared by in situ Zn(OH)42− deposition onto the surface. This novel structure has been proven to accelerate the kinetics of Zn2+ transfer and deposition via the electrostatic attraction toward Zn2+ rather than the hydrated one in the electrical double layer. As a consequence, it achieves an average 99.55% Zn utilization and long-time stability for 1000 cycles. Meanwhile, the Zn@ZnO-3D/MnO2 cell shows no capacity fading after 500 cycles at 0.5 A g−1 with a specific capacity of 212.9 mA h g−1. We believe that the mechanistic insight into the kinetics and thermodynamic properties of the Zn metal and the understanding of structure–interface–function relationships are very useful for other metal anodes in aqueous systems.

Manipulating the ion-transfer kinetics and interface stability for high-performance zinc metal anodes

https://onlinelibrary.wiley.com/doi/pdf/10.1002/eem2.12067

Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc-ion Batteries

Aqueous Zn-ion batteries (ZIBs) are promising safe energy storage systems that have received considerable attention in recent years. Based on the electrochemical behavior of Zn2+ in the charging and discharging process, herein we review the research progress on anode materials for use in aqueous ZIBs based on two aspects: Zn deposition and Zn2+ intercalation. To date, Zn dendrite, corrosion, and passivation issues have restricted the development of aqueous ZIBs. However, many strategies have been developed, including structural design, interface protection of the Zn anode, Zn alloying, and using polymer electrolytes. The main aim is to stabilize the Zn stripping/plating layer and limit side reactions. Zn2+-intercalated anodes, with a high Zn2+ storage capacity to replace the current metal Zn anode, are also a potential option. Finally, some suggestions have been put forward for the subsequent optimization strategy, which are expected to promote further development of aqueous ZIBs.

Anode Materials for Aqueous Zinc Ion Batteries: Mechanisms, Properties, and Perspectives.

With the increasing demand for large-scale energy storage, high-safety and low-cost rechargeable zinc-ion batteries (ZIBs) have been regarded as potential substitutes for lithium-ion batteries (LIB...

Xuesong Xie

Papers

Manipulating the ion-transfer kinetics and interface stability for high-performance zinc metal anodes

A Sieve-Functional and Uniform-Porous Kaolin Layer toward Stable Zinc Metal Anode

Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc-ion Batteries

Anode Materials for Aqueous Zinc Ion Batteries: Mechanisms, Properties, and Perspectives.

Electrolyte Strategies toward Better Zinc-Ion Batteries