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

Aqueous rechargeable Zn metal batteries have attracted widespread attention due to the intrinsic high volumetric capacity, low cost, and high safety. However, the low Coulombic efficiency and limited lifespan of Zn metal anodes resulting from uncontrollable growth of Zn dendrites impede their practical application. In this work, a 3D interconnected ZnF2 matrix is designed on the surface of Zn foil (Zn@ZnF2 ) through a simple and fast anodic growth method, serving as a multifunctional protective layer. The as-fabricated Zn@ZnF2 electrode can not only redistribute the Zn2+ ion flux, but also reduce the desolvation active energy significantly, leading to stable and facile Zn deposition kinetics. The results reveal that the Zn@ZnF2 electrode can effectively inhibit dendrites growth, restrain the hydrogen evolution reactions, and endow excellent plating/stripping reversibility. Accordingly, the Zn@ZnF2 electrode exhibits a long cycle life of over 800 h at 1 mA cm-2 with a capacity of 1.0 mAh cm-2 in a symmetrical cell test, the feasibility of which is also convincing in Zn@ZnF2 //MnO2 and Zn@ZnF2 //V2 O5 full batteries. Importantly, a hybrid zinc-ion capacitor of the Zn@ZnF2 //AC can work at an ultrahigh current density of ≈60 mA cm-2 for up to 5000 cycles with a high capacity retention of 92.8%.

Synergistic Manipulation of Zn2+ Ion Flux and Desolvation Effect Enabled by Anodic Growth of a 3D ZnF2 Matrix for Long‐Lifespan and Dendrite‐Free Zn Metal Anodes

Rechargeable aqueous zinc-ion batteries (RZIBs) provide a promising complementarity to the existing lithium-ion batteries due to their low cost, non-toxicity and intrinsic safety. However, Zn anodes suffer from zinc dendrite growth and electrolyte corrosion, resulting in poor reversibility. Here, we develop an ultrathin, fluorinated two-dimensional porous covalent organic framework (FCOF) film as a protective layer on the Zn surface. The strong interaction between fluorine (F) in FCOF and Zn reduces the surface energy of the Zn (002) crystal plane, enabling the preferred growth of (002) planes during the electrodeposition process. As a result, Zn deposits show horizontally arranged platelet morphology with (002) orientations preferred. Furthermore, F-containing nanochannels facilitate ion transport and prevent electrolyte penetration for improving corrosion resistance. The FCOF@Zn symmetric cells achieve stability for over 750 h at an ultrahigh current density of 40 mA cm−2. The high-areal-capacity full cells demonstrate hundreds of cycles under high Zn utilization conditions. Rechargeable aqueous zinc-ion batteries are promising but the zinc anode suffers from dendrite growth and electrolyte corrosion. Here, the authors develop a fluorinated covalent organic framework film as a protective layer for aqueous zinc anode battery.

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Horizontally Arranged Zinc Platelet Electrodeposits Modulated by Fluorinated Covalent Organic Framework Film for High-Rate and Durable Aqueous Zinc Ion Batteries

Aqueous rechargeable zinc-metal-based batteries are an attractive alternative to lithium-ion batteries for grid-scale energy-storage systems because of their high specific capacity, low cost, eco-friendliness, and nonflammability. However, uncontrollable zinc dendrite growth limits the cycle life by piercing the separator, resulting in low zinc utilization in both alkaline and mild/neutral electrolytes. Herein, a polyacrylonitrile coating layer on a zinc anode produced by a simple drop coating approach to address the dendrite issue is reported. The coating layer not only improves the hydrophilicity of the zinc anode but also regulates zinc-ion transport, consequently facilitating the uniform deposition of zinc ions to avoid dendrite formation. A symmetrical cell with the polymer-coating-layer-modified Zn anode displays dendrite-free plating/stripping with a long cycle lifespan (>1100 h), much better than that of the bare Zn anode. The modified zinc anode coupled with a Mn-doped V2 O5 cathode forms a stable rechargeable full battery. This method is a facile and feasible way to solve the zinc dendrite problem for rechargeable aqueous zinc-metal batteries, providing a solid basis for application of aqueous rechargeable Zn batteries.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.202100309

An Artificial Polyacrylonitrile Coating Layer Confining Zinc Dendrite Growth for Highly Reversible Aqueous Zinc-Based Batteries

Zn anodes suffer from poor Coulombic efficiency (CE) and serious dendrite formation due to the unstable anode/electrolyte interface (AEI). The electrical double layer (EDL) structure formed before cycling is of great significance for building stable solid electrolyte interphase (SEI) on Zn surface but barely discussed in previous research about the stabilization of Zn anode. Herein, saccharin (Sac) is introduced as electrolyte additive for regulating the EDL structure on the AEI. It is found that Sac derived anions are preferentially adsorbed on the Zn metal surface instead of water dipole, creating a new H2 O-poor EDL structure. Moreover, the unique SEI is also detected on the Zn surface due to the decomposition of Sac anions. Both are proved to be capable of modulating Zn deposition behavior and preventing side reactions. Encouragingly, Zn|Zn symmetric cells using Sac additive deliver a high cumulative plated capacity of 2.75 Ah cm-2 and a high average CE of 99.6% under harsh test condition (10 mA cm-2 , 10 mAh cm-2 ). The excellent stability is also achieved at a high rate of 40 mA cm-2 . The effectiveness of this Sac additive is further demonstrated in the Zn-MnO2 full cells.

Stabilizing Zinc Anodes by Regulating the Electrical Double Layer with Saccharin Anions.

Redirected Zn Electrodeposition by an Anti-Corrosion Elastic Constraint for Highly Reversible Zn Anodes

A “dendrite-eating” separator for high-areal-capacity lithium-metal batteries

https://onlinelibrary.wiley.com/doi/pdf/10.1002/eem2.12181

Ruirui Zhao

Papers

Redirected Zn Electrodeposition by an Anti-Corrosion Elastic Constraint for Highly Reversible Zn Anodes

A “dendrite-eating” separator for high-areal-capacity lithium-metal batteries

A Stretchable Ionic Conductive Elastomer for High-Areal-Capacity Lithium-Metal Batteries