Electrolyte Solvation Chemistry for Stabilizing the Zn Anode via Functionalized Organic Agents.

As a potential candidate for grid-scale energy storage technology, aqueous Zn-ion batteries (ZIBs) have attracted considerable attention due to their intrinsic safety, environmental friendliness, and ease of fabrication. Nevertheless, the road to industry for this technique is hindered by serious issues, including undesired side reactions, random growth of the Zn dendrites, electrode passivation, and anode corrosion, which are associated with the high reactivity of water molecules during the electrochemical reactions. These challenges are strongly dependent on electrolyte solvation chemistry (ESC), which subsequently determines the electrochemical behavior of the metal ions and water molecules on the electrode surface. In this work, a comprehensive understanding of optimized ESC with specified functional groups on the mixing agents to stabilize the Zn anode is provided. First, the challenges facing the ZIBs and their chemical principles are outlined. Specific attention is paid to the working principles of the mixing agents with different functional groups. Then the recent progress is summarized and compared. Finally, perspectives on future research for the aqueous Zn batteries are presented from the point of view.

A Crystalline-Water Electrolyte Enabled High Depth-of-Discharge Anodes in Aqueous Zinc Metal Batteries.

Aqueous zinc metal batteries are regarded as a promising energy storage solution for a green and sustainable society in the future. However, the practical application of metallic zinc anode is plagued by the thermodynamic instability issue of water molecules in conventional electrolytes, which leads to severe dendrite growth and side reactions. In this work, an ultra-thin and high areal capacity metallic zinc anode is achieved by utilizing crystalline water with a stable stoichiometric ratio. Unlike conventional electrolytes, the designed electrolyte can effectively suppress the reactivity of water molecules and diminish the detrimental corrosion on the metallic zinc anode, while preserving the inherent advantages of water molecules, including great kinetic performance in electrolytes and H+ capacity contribution in cathodes. Based on the comprehensive performance of the designed electrolyte, the 10 µm Zn||10 µm Zn symmetric cell stably ran for 1000 h at the current density of 1 mA cm-2, and the areal capacity of 1 mAh cm-2, whose depth-of-discharge is over 17.1%. The electrochemical performance of the 10 µm Zn||9.3 mg cm-2 polyaniline (PANI) full-cell demonstrates the feasibility of the designed electrolyte. This work provides a crucial understanding of balancing activity of water molecules in aqueous zinc metal batteries.

Cathode|Electrolyte Interface Engineering by a Hydrogel Polymer Electrolyte for a 3D Porous High-Voltage Cathode Material in a Quasi-Solid-State Zinc Metal Battery by In Situ Polymerization.

This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14 Wh kg-1 with that of its liquid counterpart (240.38 Wh kg-1, 0.5 M Zn(CF3SO3)2 aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0 A g-1, compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.

Interlayer Space Engineering-Induced Pseudocapacitive Zinc-Ion Storage in Holey Graphene Oxide-Bearing Vertically Oriented MoS2 Nano-Wall Array Cathode for Aqueous Rechargeable Zn Metal Batteries.

Transition metal dichalcogenides, particularly MoS2, are acknowledged as a promising cathode material for aqueous rechargeable zinc metal batteries (ARZMBs). Nevertheless, its lack of hydrophilicity, poor electrical conductivity, significant restacking, and restricted interlayer spacing translate into inadequate capacity and rate performance. Herein, the unique porous structure and additional functional groups present in holey graphene oxide (hGO) are taken advantage of to dictate the vertical growth pattern of oxygen-doped MoS2 nanowalls (O-MoS2/NW) over the hGO surface. Compared to conventional graphene oxide (GO), the presence of nano-pores in hGO facilitates the homogeneous dispersion of Mo precursors and provides stronger interaction sites, promoting the uniform vertical alignment of O-MoS2/NW. The synergistic interaction between O-MoS2-NW and hGO translates to enhanced electron conductivity, efficient electrolyte penetration, enhanced interlayer spacing, reduced restacking, and enhanced surface area. As a consequence of precise control of various factors that decide the overall battery performance, a high discharge capacity (227 mAh g-1 at 100 mA g-1) cathode material with significantly lower charge transfer resistance (66 Ω) compared to pristine O-MoS2 (153 Ω) is developed. These findings underscore the potential of hGO as a multifunctional platform for nanoengineering high-performance cathode materials for the next generation of efficient and durable ARZMBs.

Physicochemical Synergistic Separator Coating Induces Uniform and Rapid Deposition of Li and Zn Ions.

Li and Zn metal batteries are the most promising candidates to replace conventional Li-ion batteries. However, a series of issues, especially dendrites caused by uneven deposition of cations during charge-discharge cycles, hinder their practical application. Here, we proposed a facile separator modification method which combines physical and chemical forces to regulate uniform and rapid deposition of both Li+ and Zn2+. Physically, the electronegativity of modified separators drives rapid transport of metal ions via a surface diffusion mode. Chemically, the polar surface functional groups on coated separators induce uniform deposition of metal ions so that the dendrite growth is effectively inhibited. As a result, the Li and Zn metal anodes employing modified separators can cycle stably for over 1000 h under a large current density of 10 mA cm-2.

Building Sustainable Saturated Fatty Acid-Zinc Interfacial Layer toward Ultra-Stable Zinc Metal Anodes.

The commercialization pace of aqueous zinc batteries (AZBs) is seriously limited due to the uncontrolled dendrite growth and severe corrosion reaction of the zinc anode. Herein, a universal and extendable saturated fatty acid-zinc interfacial layer strategy for modulating the interfacial redox process of zinc toward ultrastable Zn metal anodes is proposed. The in situ complexing of saturated fatty acid-zinc interphases could construct an extremely thin zinc compound layer with continuously constructed zincophilic sites which kinetically regulates Zn nucleation and deposition behaviors. Furthermore, the multifunctional interfacial layer with internal hydrophobic carbon chains as a protective layer is efficient to exclude active water molecules from the surface and efficiently inhibit the surface corrosion of zinc. Consequently, the modified anode shows a long cycle life of over 4000 h at 5 mA cm-2. In addition, the assembled Zn||V2O5 full cells based on modified zinc anodes have excellent rate performance and long cycle stability.

Ionic Layer Epitaxy Growth of Organic/Inorganic Composite Protective Layers for Large-Area Li and Zn Metal Anodes.

Li and Zn metal batteries using organic and aqueous electrolytes, respectively, are desirable next-generation energy storage systems to replace the traditional Li-ion batteries. However, their cycle life and safety performance are severely constrained by a series of issues that are attributed to dendrite growth. To solve these issues, a nanothick ZnO-oleic acid (ZnO-OA) composite protective layer is developed by a facile ionic layer epitaxy method. The ZnO-OA layer provides strong lithophilic and zincophilic properties, which can effectively induce uniform ion deposition. As a result, the ZnO-OA protected Li and Zn metal anodes can cycle stably for over 600 and 1000 h under a large current density of 10 mA cm-2. Employing the ZnO-OA protected anodes, the Li||LiFePO4 cell can maintain a capacity retention of 99.5% after 600 cycles at a 1 C rate and the Zn||MnO2 cell can operate stably for 1000 cycles at 1 A g-1 current density.

Interfacial Engineering for Oriented Crystal Growth toward Dendrite-Free Zn Anode for Aqueous Zinc Metal Battery.

Zn deposition with a surface-preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag-modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP-Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion-resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high-performance aqueous zinc metal batteries.

Zincophilic Sites Enriched Hydrogen-Bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries.

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen-bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA-BTA@Zn). The framework with abundant H-bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte-philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, -NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating-associated stress. The MA-BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm-2. The MA-BTA@Zn||Cu half-cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5 % at 10 mA cm-2.

For Zinc Metal Batteries, How Many Electrons go to Hydrogen Evolution? An Electrochemical Mass Spectrometry Study.

Despite the advantages of aqueous zinc (Zn) metal batteries (AZMB) like high specific capacity (820 mAh g-1 and 5,854 mAh cm-3 ), low redox potential (-0.76 V vs. the standard hydrogen electrode), low cost, water compatibility, and safety, the development of practically relevant batteries is plagued by several issues like unwanted hydrogen evolution reaction (HER), corrosion of Zn substrate (insulating ZnO, Zn(OH)2 , Zn(SO4 )x (OH)y , Zn(ClO4 )x (OH)y etc. passivation layer), and dendrite growth. Controlling and suppressing HER activity strongly correlates with the long-term cyclability of AZMBs. Therefore, a precise quantitative technique is needed to monitor the real-time dynamics of hydrogen evolution during Zn electrodeposition. In this study, we quantify hydrogen evolution using in situ electrochemical mass spectrometry (ECMS). This methodology enables us to determine a correction factor for the faradaic efficiency of this system with unmatched precision. For instance, during the electrodeposition of zinc on a copper substrate at a current density of 1.5 mA/cm2 for 600 seconds, 0.3 % of the total charge is attributed to HER, while the rest contributes to zinc electrodeposition. At first glance, this may seem like a small fraction, but it can be detrimental to the long-term cycling performance of AZMBs. Furthermore, our results provide insights into the correlation between HER and the porous morphology of the electrodeposited zinc, unravelling the presence of trapped H2 and Zn corrosion during the charging process. Overall, this study sets a platform to accurately determine the faradaic efficiency of Zn electrodeposition and provides a powerful tool for evaluating electrolyte additives, salts, and electrode modifications aimed at enhancing long-term stability and suppressing the HER in aqueous Zn batteries.

Tetraphenylporphyrin-based Chelating Ligand Additive as a Molecular Sieving Interfacial Barrier toward Durable Aqueous Zinc Metal Batteries.

The sustained water consumption and uncontrollable dendrite growth strongly hamper the practical applications of rechargeable zinc (Zn) metal batteries (ZMBs). Herein, for the first time, we demonstrate that trace amount of chelate ligand additive can serve as a "molecular sieve-like" interfacial barrier and achieve highly efficient Zn plating/stripping. As verified by theoretical modeling and experimental investigations, the benzenesulfonic acid groups on the additive molecular not only facilitates its water solubility and selective adsorption on the Zn anode, but also effectively accelerates the de-solvation kinetics of Zn2+ . Meanwhile, the central porphyrin ring on the chelate ligand effectively expels free water molecules from Zn2+ via chemical binding against hydrogen evolution, and reversibly releases the captured Zn2+ to endow a dendrite-free Zn deposition. By virtue of this non-consumable additive, high average Zn plating/stripping efficiency of 99.7 % over 2100 cycles together with extended lifespan and suppressed water decomposition in the Zn||MnO2 full battery were achieved, thus opening a new avenue for developing highly durable ZMBs.

An Ultrathin Inorganic Molecular Crystal Interfacial Layer for Stable Zn Anode.

Zn metal anode suffers from dendrite growth and side reactions during cycling, significantly deteriorating the lifespan of aqueous Zn metal batteries. Herein, we introduced an ultrathin and ultra-flat Sb2 O3 molecular crystal layer to stabilize Zn anode. The in situ optical and atomic force microscopes observations show that such a 10 nm Sb2 O3 thin layer could ensure uniform under-layer Zn deposition with suppressed tip growth effect, while the traditional WO3 layer undergoes an uncontrolled up-layer Zn deposition. The superior regulation capability is attributed to the good electronic-blocking ability and low Zn affinity of the molecular crystal layer, free of dangling bonds. Electrochemical tests exhibit Sb2 O3 layer can significantly improve the cycle life of Zn anode from 72 h to 2800 h, in contrast to the 900 h of much thicker WO3 even in 100 nm. This research opens up the application of inorganic molecular crystals as the interfacial layer of Zn anode.

Trigger a multi-electron reaction by tailoring electronic structure of VO2 toward more efficient aqueous zinc metal batteries.

VO2 (B) is recognized as a promising cathode material for aqueous zinc metal batteries (AZMBs) owing to its remarkable specific capacity and its unique, expansive tunnel structure, which facilitates the reversible insertion and extraction of Zn2+. Nonetheless, challenges such as the inherent instability of the VO2 structure, poor ion/electron transport and a limited capacity due to the low redox potential of the V3+/V4+ couple have hindered its wider application. In this study, we present a strategy to replace vanadium ions by doping Al3+ in VO2. This approach activates the multi-electron reaction (V4+/V5+), to increase the specific capacity and improve the structural stability by forming robust V5+O and Al3+O bonds. It also induces a local electric field by altering the local electron arrangement, which significantly accelerates the ion/electron transport process. As a result, Al-doped VO2 exhibits superior specific capacity, improved cycling stability, and accelerated electronic transport kinetics compared to undoped VO2. The beneficial effects of heterogeneous atomic doping observed here may provide valuable insights into the improvement electrode materials in metal-ion battery systems other than those based on Zn.

Superfast Zincophilic Ion Conductor Enables Rapid Interfacial Desolvation Kinetics for Low-Temperature Zinc Metal Batteries.

Low-temperature rechargeable aqueous zinc metal batteries (AZMBs) as highly promising candidates for energy storage are largely hindered by huge desolvation energy barriers and depressive Zn2+ migration kinetics. In this work, a superfast zincophilic ion conductor of layered zinc silicate nanosheet (LZS) is constructed on a metallic Zn surface, as an artificial layer and ion diffusion accelerator. The experimental and simulation results reveal the zincophilic ability and layer structure of LZS not only promote the desolvation kinetics of [Zn(H2O)6]2+ but also accelerate the Zn2+ transport kinetics across the anode/electrolyte interface, guiding uniform Zn deposition. Benefiting from these features, the LZS-modified Zn anodes showcase long-time stability (over 3300 h) and high Coulombic efficiency with ≈99.8% at 2 mA cm-2, respectively. Even reducing the environment temperature down to 0 °C, ultralong cycling stability up to 3600 h and a distinguished rate performance are realized. Consequently, the assembled Zn@LZS//V2O5-x full cells deliver superior cyclic stability (344.5 mAh g-1 after 200 cycles at 1 A g-1) and rate capability (285.3 mAh g-1 at 10 A g-1) together with a low self-discharge rate, highlighting the bright future of low-temperature AZMBs.

"Water-in-Salt" Electrolyte Suppressed MnVOPO4·2H2O Cathode Dissolution for Stable High-Voltage Platform and Cycling Performance for Aqueous Zinc Metal Battery.

Vanadium-based materials have the advantages of abundant valence states and stable structures, having great application potential as cathode materials in metal-ion batteries. However, their low voltage and vanadium dissolution in traditional water-based electrolytes greatly limit their application and development in aqueous zinc metal batteries (AZMBs). Herein, phosphate- and vanadium-based cathode materials (MnVOPO4·2H2O) with stacked layers and few defects were prepared via a condensation reflux method and then combined with a high-concentration electrolyte (21 m LiTFSI + 1 M Zn(CF3SO3)2) to address these limitations. The specific capacity and cycle stability accompanying the stable high voltage of 1.39 V were significantly enhanced compared with those for the traditional electrolyte of 3 M Zn(CF3SO3)2, benefiting from the suppressed vanadium dissolution. The cathode materials of MnVOPO4·2H2O achieved a high specific capacity of 152 mAh g-1 at 0.2 A g-1, with a retention rate of 86% after 100 cycles for AZMBs. A high energy density of 211.78 Wh kg-1 was also achieved. This strategy could illuminate the significance of electrolyte modification and provide potential high-voltage cathode materials for AZMBs and other rechargeable batteries.

Phase-Field Simulation of a Dynamic Protective Layer for the Inhibition of Dendrite Growth in Zinc Metal Batteries.

Metallic zinc (Zn) has been considered one of the most promising anode materials for next-generation aqueous Zn batteries due to its low redox potential and high storage capacity. However, excessive dendrite formation in Zn metal, corrosion, the evolution of hydrogen gas during the cycling process, and the poor Zn-ion (Zn2+) transport from the electrolyte to the electrode limit its practical application. One of the most effective strategies to suppress Zn dendrite growth and promote Zn2+ transport is to introduce suitable protective layers between the Zn metal electrode and the electrolyte. Herein, we mathematically simulated the dynamic interactions between the Zn deposition on the anode and the resulting displacement of a protective layer that covers the anode, the latter of which can simultaneously inhibit Zn dendrite growth and enhance the Zn2+ transport through the interface between the Zn anode and the protective layer. Our simulation results indicate that a protective layer of high Zn2+ diffusivity not only improves the deposition rate of the Zn metal but also prevents dendrite growth by homogenizing the Zn2+ concentration at the anode surface. In addition, it is revealed that the anisotropic Zn2+ diffusivity in the protective layer influences the 2D diffusion of Zn2+. Higher Zn2+ diffusivity perpendicular to the Zn metal surface inhibits dendrite growth, while higher diffusivity parallel to the Zn metal surface promotes dendrite growth. Our work thus provides a fundamental understanding and a design principle for controlling anisotropic Zn2+ diffusion in the protective layer for better suppression of dendrite growth in Zn metal batteries.

Stable Zn Metal Anodes with Limited Zn-Doping in MgF2 Interphase for Fast and Uniformly Ionic Flux.

The practical applications of aqueous Zn metal batteries are currently restricted by the inherent drawbacks of Zn such as the hydrogen evolution reaction, sluggish kinetics, and dendrite formation. To address these problems, herein, a limitedly Zn-doped MgF2 interphase comprising an upper region of pure, porous MgF2 and a lower region of gradient Zn-doped MgF2 is achieved via radio frequency sputtering technique. The porous MgF2 region is a polar insulator whose high corrosion resistance facilitates the de-solvation of the solvated Zn ions and suppression of hydrogen evolution, resulting in Zn metal electrodes with a low interfacial resistance. The Zn-doped MgF2 region facilitates fast transfer kinetics and homogeneous deposition of Zn ions owing to the interfacial polarization between the Zn dopant and MgF2 matrix, and the high concentration of the Zn dopant on the surface of the metal substrate as fine nuclei. Consequently, a symmetric cell incorporating the proposed Zn metal exhibits low overpotentials of ~ 27.2 and ~ 99.7 mV without Zn dendrites over 250 to 8000 cycles at current densities of 1.0 and 10.0 mA cm-2, respectively. The developed Zn/MnO2 full cell exhibits superior capacity retentions of 97.5% and 84.0% with average Coulombic efficiencies of 99.96% after 1000 and 3000 cycles, respectively.

Working Aqueous Zn Metal Batteries at 100 °C.

Reliable power supplies at extremely high temperatures are urgently needed to broaden the application scenarios for electric devices. Aqueous zinc metal batteries (ZMBs) with intrinsic safety are a promising alterative for high-temperature energy storage. However, the reversibility and long-term cycling stability of aqueous ZMBs at extremely high temperatures (≥100 °C) have rarely been explored. Herein, we reveal that spontaneous Zn corrosion and severe electrochemical hydrogen evolution at high temperature are vital restrictions for traditional aqueous ZMBs. To address this, a crowding agent, 1,5-pentanediol, was introduced into an aqueous electrolyte to suppress water reactivity by strengthening O-H bonds of H2O and decreasing H2O content in the Zn2+ solvation sheath, while maintaining flame resistance of the electrolyte. Importantly, this electrolyte enabled reversible Zn deposition with a Coulombic efficiency of 98.1% and a long cycling life of Zn//Zn batteries for over 500 cycles (at 1 mA cm-2 and 0.5 mAh cm-2) at 100 °C. Moreover, stable cycling of Zn//Te full batteries at 100 °C was demonstrated.

A Functional Organic Zinc-Chelate Formation with Nanoscaled Granular Structure Enabling Long-Term and Dendrite-Free Zn Anodes.

Aqueous Zn metal batteries suffer from rapid cycling deterioration due to the severe water corrosion and dendrite growth on Zn anodes. Herein, a highly antiwater Znx-diethylenetriaminepenta(methylene-phosphonic acid) interface layer with good zinc affinity and special nanoscaled 3D granular structure is designed on Zn metal to address these problems. Experimental results combined with theoretical analysis and COMSOL simulations reveal that the hydrophobic groups in such Zn-based organic complex are the decisive factor in preventing H2O from damaging Zn anode surface. The massive Zn2+ attractive sites formed by interaction of methylene-phosphonic acid groups and Zn cause ion channel for fast zinc-ion adsorption and migration. And the developed nano granular architecture on the surface induces redistributed Zn2+ ion flux to realize homogenization with smooth and compact surface deposition. Under the synergism, such modified anodes exhibit long cycling lifespan over 1300 h with a relatively low polarization voltage at 5 mA cm-2. Also, the assembled full cells (including Zn//V2O5 and Zn//MnO2 cell) based on this anode are also demonstrated. The work provides a simple, low cost, and efficient pathway by combining the two concepts of structural design and constructing protective layers on the surface to prepare high-performance Zn anodes toward prospering aqueous zinc-metal batteries.

A Chemically Polished Zinc Metal Electrode with a Ridge-like Structure for Cycle-Stable Aqueous Batteries.

Aqueous rechargeable zinc (Zn) metal batteries show great application prospects in grid-scale energy storage devices due to their good safety, low cost, and considerable energy density. However, the electrical and topographical inhomogeneity caused by the native passivation layer of metallic Zn foil leads to inhomogeneous electrochemical plating and stripping of metallic Zn, and the limited accessible area to the electrolyte of the regular foil electrode causes the poor rate capability, which together hinder the practical application of the Zn metal electrode in rechargeable aqueous batteries. In this work, we show that the native passivation layer on the Zn foil electrode can be removed by a simple chemical polishing strategy, associated with the formation of a three-dimensional ridge-like structure of metallic Zn (r-Zn) on the surface of the Zn foil electrode due to the selective etching of weak crystallographic planes and grain boundary of metallic Zn. The clean and uniform surface of the metallic Zn electrode enables homogeneous plating and stripping of metallic Zn, and the ridge-like structure of r-Zn increases the accessible surface area to the electrolyte and reduces the local current density, which elevates the electrochemical performance of the Zn metal anode with regard to the cycling stability and rate capability. It is demonstrated that a r-Zn anode cycles stably for over 200 h at 1 mA cm-2 and 0.5 mA h cm-2 with a low overpotential of 20 mV, which far outperforms 39 h of cycling with an overpotential of 72 mV for its pristine metallic Zn counterpart.