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Zinc metal anodes are gaining popularity in aqueous electrochemical energy storage systems for their high safety, cost‐effectiveness, and high capacity. However, the service life of zinc metal anodes is severely constrained by critical challenges, including dendrites, water‐induced hydrogen evolution, and passivation. In this study, a protective two‐dimensional metal–organic framework interphase is in situ constructed on the zinc anode surface with a novel gel vapor deposition method. The ultrathin interphase layer (~1 μm) is made of layer‐stacking 2D nanosheets with angstrom‐level pores of around 2.1 Å, which serves as an ion sieve to reject large solvent–ion pairs while homogenizes the transport of partially desolvated zinc ions, contributing to a uniform and highly reversible zinc deposition. With the shielding of the interphase layer, an ultra‐stable zinc plating/stripping is achieved in symmetric cells with cycling over 1000 h at 0.5 mA cm−2 and ~700 h at 1 mA cm−2, far exceeding that of the bare zinc anodes (250 and 70 h). Furthermore, as a proof‐of‐concept demonstration, the full cell paired with MnO2 cathode demonstrates improved rate performances and stable cycling (1200 cycles at 1 A g−1). This work provides fresh insights into interphase design to promote the performance of zinc metal anodes. [ABSTRACT FROM AUTHOR]

The research introduces trace amounts (0.1 mM) of 2-ethyl-1H-benzimidazole (EHB) into ZnSO 4 (ZS) electrolyte, regulating the nucleation overpotential of dendrite-free ZIBs. Under the influence of EHB additives, the modified electrolyte (ZS-EHB) nucleation overpotential increased from 53.0 mV to 74.2 mV. Therefore, in the ZS-EHB electrolyte, the inhibition efficiency exceeds 90%, and achieve ultra-long cycle of Zn||Zn batteries. [Display omitted] • Economical, trace, and efficient electrolyte additive EHB (0.1 mM) achieves dendrite-free zinc anode. • The strong zincophilic hydrophobic structure of EHB is effectively adsorbed on the zinc anode to regulate nucleation overpotential. • EHB achieves high reversibility of the zinc anode. Large-scale energy storage applications can greatly benefit from the low-cost and safe zinc metal anode. However, corrosion, side reactions and dendrite growth in water significantly inhibit the cycle life of zinc-ion batteries. Here, 2-ethyl-1H-benzimidazole (EHB), a strong zincophilic and hydrophobic structure, is introduced into the ZnSO 4 (ZS) electrolyte to adjust the nucleation overpotential in Zinc-ion batteries for the initial time. The strong zincophilic side of EHB firmly adheres to the zinc anode, while the hydrophobic end further protects the zinc anode from the influence of active water molecules due to steric effect. With the addition of EHB, the nucleation overpotential of the modified electrolyte (ZS-EHB) increases from 53.0 mV to 74.2 mV at 1 mA cm−2. Consequently, the inhibition efficiency of Zn anode in ZS-EHB electrolyte exceeds 90 %, and the lifespan of the symmetric Zn||Zn cells in ZS-HEB electrolyte reaches 6200 h at 5 mA cm−2 and over 2400 h at 8 mA cm−2, nearly 80-fold longer than that of the cells in ZS electrolyte. Furthermore, the designed Zn||α-MnO 2 cells can still deliver a consistent discharge capacity of 120.1 mAh g−1 even after 500 cycles. The research offers a promising route for creating zinc anode electrolyte additives. [ABSTRACT FROM AUTHOR]

The feasibility of aqueous zinc‐ion batteries for large‐scale energy storage is hindered by the inherent challenges of Zn anode. Drawing inspiration from cellular mechanisms governing metal ion and nutrient transport, erythritol is introduced, a zincophilic additive, into the ZnSO4 electrolyte. This innovation stabilizes the Zn anode via chelation interactions between polysaccharides and Zn2+. Experimental tests in conjunction with theoretical calculation results verified that the erythritol additive can simultaneously regulate the solvation structure of hydrated Zn2+ and reconstruct the hydrogen bond network within the solution environment. Additionally, erythritol molecules preferentially adsorb onto the Zn anode, forming a dynamic protective layer. These modifications significantly mitigate undesirable side reactions, thus enhancing the Zn2+ transport and deposition behavior. Consequently, there is a notable increase in cumulative capacity, reaching 6000 mA h cm⁻2 at a current density of 5 mA cm−2. Specifically, a high average coulombic efficiency of 99.72% and long cycling stability of >500 cycles are obtained at 2 mA cm−2 and 1 mA h cm−2. Furthermore, full batteries comprised of MnO2 cathode and Zn anode in an erythritol‐containing electrolyte deliver superior capacity retention. This work provides a strategy to promote the performance of Zn anodes toward practical applications. [ABSTRACT FROM AUTHOR]

The carbon nanoparticles layer coated zinc anode with (1 0 3) crystal plane preferential oriented crystal structure (denoted as C@RZn) is prepared by a facile one-step vapor deposition method, and showed great potentials in extending lifespan and inhibiting dendrite growth. [Display omitted] • The C@RZn was prepared by a facile one-step vapor deposition method. • The C@RZn is combining crystallographic orientation and coating layer. • The C@RZn can guide the deposition of Zn2+ ions and inhibit the dendrite growth. • The C@RZn anode achieves a stable cycle life for more than 3000 h. • The MVO//C@RZn cell keep stable for 5000 cycles. Aqueous zinc ion batteries (ZIBs) have been considered promising energy storage systems due to their excellent electrochemical performance, environmental toxicity, high safety and low cost. However, uncontrolled dendrite growth and side reactions at the zinc anode have seriously hindered the development of ZIBs. Herein, we prepared the carbon nanoparticles layer coated zinc anode with (1 0 3) crystal plane preferential oriented crystal structure (denoted as C@RZn) by a facile one-step vapor deposition method. The preferential crystallographic orientation of (1 0 3) crystal plane promotes zinc deposition at a slight angle, effectively preventing the formation of Zn dendrites on the surface. In addition, the hydrophobic layer of carbon layer used as an inert physical barrier to prevent corrosion reaction and a buffer during volume changes, thus improving the reversibility of the zinc anode. As a result. the C@RZn anode achieves a stable cycle performance of more than 3000 h at 1 mA cm−2 with CE of 99.77 % at 5 mA cm−2. The full battery with C@RZn anode and Mn-doped V 6 O 13 (MVO) cathode show stability for 5000 cycles at the current density of 5 A g−1. This work provides a new approach for the design of multifunctional interfaces for Zn anode. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries represent a highly promising next‐generation electrochemical energy storage system because of their safety, environmental friendliness, resource abundance, and simple assembly conditions. However, the formation and growth of zinc dendrites on zinc anode seriously hinder the practical application of zinc‐ion batteries. Zincophilic design, which enables the uniform zinc nucleation/deposition, offers an effective solution to achieve dendrite‐free zinc anodes. Despite significant progress in the field of zincophilic design, the research in this field currently lacks clear analysis and guidance. This paper provides a comprehensive overview of the current research status of zincophilic design and the mechanism for dendrite‐free zinc anode from three aspects: construction of zinc anode zincophilic layers, addition of zincophilic additives in electrolyte, and construction of 3D zincophilic host. Moreover, the challenges facing the industrialization and commercialization of zinc‐ion batteries in the further are briefly discussed. [ABSTRACT FROM AUTHOR]

According to the first principle, the SDS anions are preferentially adsorbed on the (0 0 2) surface of the Zn anode, forming a protective layer which prevents the adsorption of free water molecules and modifies the electrode/electrolyte interface. The SDS additive significantly inhibits the contact of water molecules with the interface, reduces the generation of by-products, and effectively prevents the growth of dendrites. Consequently, with the assistance of SDS additives, the Zn||Zn symmetrical battery sustains a long cycle life for 2000h. [Display omitted] Aqueous zinc-ion batteries are emerging as powerful candidates for large-scale energy storage, due to their inherent high safety and high theoretical capacity. However, the inevitable hydrogen evolution and side effects of the deposition process limit their lifespan, which requires rational engineering of the interface between anode and aqueous electrolyte. In this paper, an anionic surfactant as electrolyte additive, sodium dodecyl sulfonate (SDS), is introduced to deliver highly reversible zinc metal batteries. Unlike traditional surfactants, the solvation structure is not affected by SDS, which tends to adsorb on the (0 0 2) crystal plane of Zn with the purpose of effectively limiting the water molecules adsorption. Attributed to the natural hydrophobic part of SDS, a dynamic electrostatic shielding layer and a unique hydrophobic interface are constructed on the anode. Assisted by the above merits, the adverse surface corrosion, hydrogen evolution and dendrite growth are significantly inhibited without the sacrifice in the deposition kinetics of Zn ions. As a result, the Zn||Zn symmetric batteries demonstrate an increased cycle life of 2000 h (1 mA cm−2, 1 mA h cm−2) with the presence of SDS additive. Such strategy provides a new avenue for the developing advanced electrolytes to be applied in aqueous energy storage systems. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries are promising for next‐generation energy storage systems. However, the zinc dendrite growth, corrosion, and hydrogen evolution reaction at the electrochemical interface severely impede their further development. Herein, a Zn2+‐rich and H2O‐poor Helmholtz plane is constructed to regulate the electrochemical interface between the zinc anode and the electrolyte. Electrochemical and in situ spectroscopy characterizations reveal that the designed electric double layer with abundant Zn2+ coordination sites and less H2O content can facilitate rapid electron transfer, homogenize Zn2+ deposition, and alleviate the side reactions induced by active H2O. Benefiting from the high reversibility and stability of zinc anode, the Zn||Zn symmetric cell can be cycled over 1000 h at 1 mA cm−2 and the Zn||NH4V4O10 full cell can maintain a capacity of 85.23% for 1000 cycles at 3 A g−1. This work aims at Helmholtz plane reconfiguration and provides a realizable strategy in interface construction for other similar systems. [ABSTRACT FROM AUTHOR]

With the development of social industrialization, energy issues have become a hot topic at present. Traditional lithium-ion batteries, due to their poor safety and high cost, cannot meet the current application needs in the energy storage field in the long term. Therefore, the development of suitable new energy has aroused people's deep thinking. Aqueous zinc-ion batteries (AZIBs) have attracted attention from the scientific research community in recent years due to their high safety, cleanliness, and other advantages. However, dendrites are easily grown on the zinc anode, and free water molecules can also corrode the zinc anode, causing side reactions such as hydrogen evolution and passivation, seriously affecting the long-term cycling performance and stability of the battery. This work introduces a new type of ionic liquid additive 1-cyanobutyl-3-methylimidazole chloride (MCBI) to optimize aqueous electrolytes. Before the deposition of zinc ions on the anode surface, MCBI cations will preferentially land on the anode. Due to their special structures of Electron-withdrawing group and nitrogen heterocycles, they will tightly adsorb on the zinc surface in a unique shape of the “Check mark” posture. This provides abundant sites for the deposition of zinc ions, allowing zinc atoms to arrange regularly between MCBI ions, thereby reducing the generation of dendrites. Due to the steric hindrance effect, by-products (Zinc hydroxide sulfate) will also accumulate in an orderly manner around additive ions, forming channels for uniform deposition of zinc ions; The hydrophobic alkyl groups of MCBI cations will repel most of the free water molecules outside the anode, thereby reducing hydrogen evolution reaction (HER). In this work, under the optimal concentration conditions, the Coulomb efficiency of Zn//Cu asymmetric cell with MCBI additive can reach 99. 37% after 200 cycles; Zn//Zn symmetric batteries can stably cycle for more than 1600 h at low current density (0. 5 mA/cm2), and can cycle for more than 1000 h at 10 mA/cm², 5 mA·h/cm². Finally, VO2 as the cathode maintains a high-capacity retention rate of 88. 5% after 500 cycles in the full battery. This work provides new ideas for the anode modification strategy of aqueous zinc ion batteries. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐based energy storage devices have competitive advantages such as high power density, good safety, and wide source. However, because of the direct touch among zinc anode and aqueous electrolyte, dendrite growth and electrode side reactions are easy to occur in the plating and striping process, which seriously hinders the further development of aqueous zinc‐based energy storage devices. Therefore, it is urgent to solve the above problems to expand the existing energy storage devices. In this work, by adding an imidazo[1,2‐b]pyridazine (IP) electrolyte additive, the dendrites' growth and corrosion on the zinc anode surface could be effectively inhibited by the shielding‐anchoring double effects, which are verified by the comprehensive in situ and ex situ characterization techniques as well as the theoretical calculation support. Accordingly, the IP‐based electrolyte encourages extremely high stable zinc anode (cycling 2200 h at 1 mA cm−2) with high average Coulombic efficiency (98.72%). Moreover, the IP‐based Zn‐V2O5 full battery also exhibits excellent reversible capacity, reaching 160.8 mAh g−1 after 400 cycles at 2 A g−1. Through a straightforward alteration to the Zn anode surface, this study considerably enhances the use of highly stable and secure aqueous zinc‐ion batteries. [ABSTRACT FROM AUTHOR]

The trivalent Gd3+ ions are introduced as electrolyte additives to form an electrostatic shielding layer on the surface of the zinc anode, resulting in a highly stable and reversible zinc metal anode. [Display omitted] • The Gd3+ ions can form an electrostatic shielding layer on the zinc anode to promote the uniform deposition of Zn2+ ions. • The adsorbed Gd3+ ions acted as a buffer interface, reducing the direct contact between the zinc anode and H 2 O and thus inhibiting the interfacial parasitic reaction. • The Zn//Zn and Zn//MnO 2 cells exhibit extended cycle life and enhanced rate capability. Aqueous zinc-ion batteries (AZIBs) have become an ideal candidate for large-scale energy storage systems owing to their inherent safety and highly competitive capacity. However, severe dendrite growth and side reactions on the surface of zinc metal anodes lead to quick performance deterioration, seriously impeding the commercialization of AZIBs. In this work, a self-regulated zinc metal/electrolyte interface is constructed to solve these problems by incorporating the trivalent Gd3+ additive with a lower effective reduction potential into the aqueous ZnSO 4 electrolyte. It is revealed that the inert Gd3+ ions preferentially adsorb on the active sites of the zinc anode, and the induced electrostatic shielding layer is beneficial to uniform Zn deposition. Meanwhile, the adsorbed Gd3+ ions act as a buffer interface to lower the direct contact of the zinc anode with water molecules, thereby suppressing the interfacial parasitic reaction. These features endow the Zn//Zn battery using 0.2 M Gd3+ ions with 2940 h of cycling life at 5 mA cm−2 and a cumulative plating capacity (CPC) of 6.2 Ah cm−2 at 40 mA cm−2. When assembling with a MnO 2 cathode, the full cell using the modified electrolyte exhibits a high capacity of 268.9 mAh/g at 0.2 A/g, as well as improved rate capability and cycle stability. The results suggest the great potential of a rare earth ion additive in reinforcing Zn metal anodes for developing practical AZIBs. [ABSTRACT FROM AUTHOR]

The rapid advancement of wearable devices and flexible electronics has spurred an increasing need for high-performance, thin, lightweight, and flexible energy storage devices. In particular, thin and lightweight zinc-ion batteries require battery materials that possess exceptional flexibility and mechanical stability to accommodate complex deformations often encountered in flexible device applications. Moreover, the development of compact and thin battery structures is essential to minimize the overall size and weight while maintaining excellent electrochemical performance, including high energy density, long cycle life, and stable charge/discharge characteristics, to ensure their versatility across various applications. Researchers have made significant strides in enhancing the battery's performance by optimizing crucial components such as electrode materials, electrolytes, separators, and battery structure. This review provides a comprehensive analysis of the design principles essential for achieving thinness in zinc-ion batteries, along with a summary of the preparation methods and potential applications of these batteries. Moreover, it delves into the challenges associated with achieving thinness in zinc-ion batteries and proposes effective countermeasures to address these hurdles. This review concludes by offering insights into future developments in this field, underscoring the continual advancements and innovations that can be expected. [ABSTRACT FROM AUTHOR]

Aqueous zinc-based energy storage systems (Zn-ESSs) with intrinsic safety and good electrochemical performance are promising power suppliers for flexible electronics, whereas unstable zinc anodes especially in flexible Zn-ESSs pose a challenge. Herein, a self-assembled robust interfacial layer to achieve stable zinc anodes in non-flexible and flexible Zn-ESSs is reported. Specifically, zinc anodes and their slowly-released Zn2+ simultaneously interact with tannic acid molecules in ethanol-water solutions, triggering the self-assembly of a tannic acid/Zn2+ complex interfacial layer (CIL) that firmly anchors on the zinc anodes. The CIL containing abundant carboxyl and phenolic hydroxyl functional groups provides rich zincophilic sites to homogenize Zn2+ flux and accelerate Zn2+ desolvation-deposition, and traps H+/H2O species to prevent them from corroding zinc anodes, thereby stabilizing the zinc deposition interface. Consequently, the CIL@Zn anodes present superior stability with an operation lifetime exceeding 700 h even at 5 mA cm-2 (28 times longer than that of bare zinc anodes) and ultrahigh cumulative plated capacity of ≈1.8 Ah cm-2. The firm anchoring of the CIL enables the CIL@Zn anodes to endure diverse deformations, thus realizing highly flexible CIL@Zn anode-based Zn-ESSs. This work provides thinking in designing stable and flexible zinc anodes, promoting the development of flexible zinc-based energy storage. [ABSTRACT FROM AUTHOR]

The growing environmental pollution issues and continuous energy dilemma call for high‐performance energy storage systems (ESSs). While the inevitable safety concerns appear and restrict the application of lithium‐ion batteries in large‐scale ESSs. Contrastively, zinc ion batteries (ZIBs) attract increasing attention due to the inherent advantages of high safety, low cost, and environmental friendliness. However, the poor stability and reversibility of Zn anodes bring severe difficulty for its practical application. Considerable efforts are devoted in the anode modification, such as electrolyte adjustment, interfacial engineering, and anode structure design, but there is still a fuzzy field concerning the reaction process, regulation mechanism, and modified effect. Reviewing the history, the development of various electrodes greatly depends on the breakthrough in advanced characterization technologies, while the summarizations of technological advances in the Zn anode are still deficient. Hence, this review concentrates on the recent progress in various characterization techniques and related strategies of anode protection. The information is especially highlighted that each technique can offer the crucial or auxiliary role they play in proving specific issues. Furthermore, the opinions on current limitations and future directions of common characterization techniques are also discussed in detail, aiming to give a comprehensive perspective in designing advanced zinc anodes. [ABSTRACT FROM AUTHOR]

Zinc (Zn) aqueous batteries have gained significant research interest for large‐scale electrochemical energy storage applications due to their rich abundance of raw materials, high energy density, environmental friendliness, low capital, and maintenance expenditure. However, the progress of metallic Zn anode in the aqueous Zn battery chemistry is hindered by several critical challenges, including low Coulombic efficiency and the formation of Zn dendrites, irrespective of the pH of the electrolyte. Herein, the application of porous activated carbon (AC) derived from waste corn husk as Zn anode constituent to improve the cyclability of the aqueous Zn battery is reported. In the full cell study, it is observed that the battery containing 15 wt% of AC as anode coupled with α‐MnO2 nanorods cathode shows excellent capacity retention of 86.42% (initial discharge capacity = 211.67 mAh g−1) after 125 charge/discharge cycles at current rate of 100 mA g−1. Moreover, herein, insights into converting waste to energy by utilizing the biowaste precursor to develop stable and durable rechargeable aqueous Zn‐based batteries are provided. [ABSTRACT FROM AUTHOR]

Highlights: Detailed discussion and summary of aqueous electrolyte chemistry, parasitic reactions chemistry, and storage energy chemistry and their relationship in aqueous zinc ions batteries are conducted. The recent development of strategies for enhancing the inherent stability of electrolyte and zinc anode to restrain parasitic reactions is reviewed from a thermodynamic perspective. The regulation strategies of electrolyte/electrode interfaces to block parasitic reactions by adsorbents and solid electrolyte interphase are reviewed from a kinetic perspective. Based on the attributes of nonflammability, environmental benignity, and cost-effectiveness of aqueous electrolytes, as well as the favorable compatibility of zinc metal with them, aqueous zinc ions batteries (AZIBs) become the leading energy storage candidate to meet the requirements of safety and low cost. Yet, aqueous electrolytes, acting as a double-edged sword, also play a negative role by directly or indirectly causing various parasitic reactions at the zinc anode side. These reactions include hydrogen evolution reaction, passivation, and dendrites, resulting in poor Coulombic efficiency and short lifespan of AZIBs. A comprehensive review of aqueous electrolytes chemistry, zinc chemistry, mechanism and chemistry of parasitic reactions, and their relationship is lacking. Moreover, the understanding of strategies for suppressing parasitic reactions from an electrochemical perspective is not profound enough. In this review, firstly, the chemistry of electrolytes, zinc anodes, and parasitic reactions and their relationship in AZIBs are deeply disclosed. Subsequently, the strategies for suppressing parasitic reactions from the perspective of enhancing the inherent thermodynamic stability of electrolytes and anodes, and lowering the dynamics of parasitic reactions at Zn/electrolyte interfaces are reviewed. Lastly, the perspectives on the future development direction of aqueous electrolytes, zinc anodes, and Zn/electrolyte interfaces are presented. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous zinc‐ion batteries (ZIB) sparked a considerable surge of research attention in energy storage systems due to its environment benignity and superior electrochemical performance. Up to now, less efforts to delve into mechanisms of zinc metal anode and their electrochemical performance. Zn metal anodes sustain thorny issues with Zn dendrite growth, hydrogen evolution reaction, and Zn corrosion irreversible byproduct formation, which results in low coulomb efficiency (CE) and poor cycle ability of the battery. Herein, we reveal the fundamental understanding of the above issue, outline four step, including mass transfer, desolvation process, charge transfer and Zn cluster formation. It can be clearly seen from reported strategies to promote Zn anode stability that deals with one or more steps, thereby boosting the understanding of the issues of Zn anodes and benefiting the rational design to surmount the issue. We also sum up advanced materials and structure design such as the design of the anode surface and internal structure, electrolyte strategies, and multifunctional separators. Finally, possible tactics and future innovation direction for Zn‐based batteries are proposed to achieve high performance aqueous Zinc‐ion batteries. [ABSTRACT FROM AUTHOR]

Zinc‐ion battery has become a research hotspot in the energy storage field due to its low cost, high safety, and environmental friendliness. However, zinc as an anode has some problems such as dendrites and hydrogen evolution on the surface, which hinder the practical application of zinc. These problems are closely related to the platting and stripping behavior of zinc at the electrode interface. The construction of an artificial interface layer is one of the most direct and effective methods to protect the zinc anode, which is helpful to improve the cycle life and utilization of the zinc anode. Here, we systematically review the progress and practical significance of artificial interfacial layers in terms of uniform ion transport, inhibition of side reactions and mechanical stability. Three design principles of the artificial interface layer are summarized to guide the further research, and to bring enlightenment for the construction of practical and efficient metal zinc anode. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries (AZIBs) are of the most potential energy storage systems for large-scale applications due to their low redox potential (−0.76 V vs standard hydrogen electrode, SHE), high theoretical specific capacity (820 mA h g−1 and 5855 mA h cm−3), safety, low toxicity and price, eco-friendliness and abundant reserves. In spite of many hurdles before their practical application, great progress has been achieved on high-performance AZIBs. In this review, the main issues and their root causes faced by metal zinc anode and manganese dioxide cathode of AZIBs are analyzed, and the recent research progress on the modification strategies and their working mechanisms of both metal zinc anode and manganese dioxide cathode are focused on, and their challenges and future development prospects are also proposed, which provide a perspective for high-performance AZIBs, and further promote their practical process. • Modification strategies of both zinc anode and MnO 2 -based cathode were reviewed. • Issues of zinc dendrite, HER and corrosion for zinc anode were analyzed. • Surface coating, alloying and electrolyte additives were reviewed for metal Zn anode. • Structural engineering, doping and surface coating were reviewed for MnO 2 cathode. • Challenges of both zinc anode and MnO 2 -based cathode were proposed. [ABSTRACT FROM AUTHOR]

Aqueous zinc batteries (AZBs) show great promise for cost-effective, high-safety, and large-scale energy storage. Yet, corrosion and dendrite formation at the Zn anode interface undermine its stability, shortening the cycle life. In this work, a fluorosilane-modified metal-organic framework layer (F-MOF) is successfully prepared as a multifunctional ion-conductive interface to stabilize the Zn anode. The designed MOF-based artificial layer provides a uniform pathway for Zn deposition, while its hydrophobic nature prevents negative effects such as hydrogen evolution and corrosion. According to density functional theory (DFT) calculations, the hydration energy of Zn2+ in F-MOF@Zn(002) is reduced while the adsorption energy for Zn2+ is increased. This facilitates the desolvation process on the Zn anode surface, promoting uniform Zn deposition. Consequently, the lifespan of the F-MOF-coated Zn anode extends beyond 2000 h at a current density of 1 mA cm−2 (areal capacity: 0.5 mAh cm−2), significantly outlasting both bare Zn (225 h) and MOF-coated Zn (751 h) anodes. Additionally, the assembled coin cells and pouch-type full cells prove the practical availability of F-MOF@Zn anodes for AZBs. The F-MOF@Zn//MnO 2 full cell maintains a high-capacity retention exceeding 91.9 % even after 1000 cycles. This work highlights the practical application potential of hydrophobic MOF coatings for AZBs. [Display omitted] MOF features well-defined ion transport channels that facilitate Zn2+ diffusion, aiding in partially impeding the formation of Zn dendrites at the MOF@Zn anode. However, H 2 O ingress triggers irreversible HER on Zn electrodes, leading to their corrosion. The F-MOF@Zn anode, grafted with long-chain FAS, not only provides uniform pathways for Zn2+ but also serves as a hydrophobic buffer, separating active Zn2+ from the electrolyte [Zn(H 2 O) 6 ]2+, suppressing HER, and minimizing the accumulation of Zn 4 SO 4 (OH) 6 ·xH 2 O and hydrogen bubbles, thereby enhancing corrosion resistance. [Display omitted] • The FAS on F-MOF@Zn ensures uniform Zn2+ channels, preventing HER and corrosion. • DFT calculations show F-MOF enhances Zn2+ transport by disrupting [Zn(H 2 O) 6 ]2+ solvation. • Bare Zn and MOF@Zn symmetrical pouch batteries expands due to HER, while F-MOF@Zn pouch batteries remains stable. • The pouch cells of F-MOF@Zn lighting a bulb and maintaining high capacity after many cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] Zn-based electrochemical energy storage (EES) systems are plagued by the uncontrollable generation of dendritic zinc and side reactions on zinc anodes. Herein, we report a ZnO porous sheets-assembled sieve-like interface to stabilize zinc anodes. Specifically, ZnO porous sheets are synthesized through the thermal decomposition of basic zinc sulfate nanoflakes and then served as an artificial zinc anode-electrolyte interface. Benefiting from the sieve-like interface formed by the ZnO porous sheets, Zn2+ flux is effectively homogenized during the zinc plating process and thus zinc dendrite growth is restricted. Meanwhile, the corrosion behavior of zinc anodes is alleviated thanks to the hydrophobic feature of the ZnO porous sheets. As a result, the electrochemical properties of zinc anodes are notably optimized under the protection of such a sieve-like interface. Cycling life evaluated at 1 mA cm−2 of the zinc anodes is prolonged from less than 100 h for bare zinc anodes to 2800 h for the protected zinc anodes (Zn@ZnO), and even at 5 mA cm−2, the latter ones can operate normally for 400 h. As expected, the cycling life of VO 2 //Zn@ZnO zinc-ion batteries is greatly increased, achieving 90% capacity retention after 1000 cycles at 5 A g−1 and activated carbon fiber//Zn@ZnO zinc-ion hybrid supercapacitors possess 96% capacity retention after 10,000 cycles at 1 A g−1. This work provides a promising approach for improving the electrochemical stability of the Zn-based EES system. [ABSTRACT FROM AUTHOR]

Zinc‐ion batteries are regarded as an extremely promising candidate for large‐scale energy storage equipment due to the inexpensive ingredients and high safety. However, dendrite growth and side reactions occur in the Zn anode, which lead to exceedingly low coulombic efficiency (CE) and poor cycling stability. In this work, we propose a strategy of a conductive/insulating bi‐functional coating layer (CIBL) for stable Zn metal anodes. Porous Ag nanowires (NWs) coating as a conductive layer effectively reduces the nuclear barrier and contains Zn2+ deposition in a certain space. Polyimide (PI) coatings as insulating layer implement a shunting effect on Zn2+, which could reduce the differential concentration on the Zn surface and induce uniform deposition of Zn2+. Therefore, the CIBL−Zn//CIBL−Zn battery achieves stable plating/stripping of over 1300 h at 1 mA cm−2. The CE of CIBL−Zn//CIBL−Zn battery maintains at 99.2 % even after 1000 cycles. Moreover, the CIBL−Zn//V2O5 battery exhibits a capacity of nearly 289.2 mA h g−1 at 5 A g−1 after 3000 cycles and no sign of capacity degradation is found, which further demonstrate the feasibility of this strategy in practical application. [ABSTRACT FROM AUTHOR]

As a sustainable, safe, and cost-effective alternative to conventional lithium-ion batteries, aqueous rechargeable zinc-metal-based batteries have attracted significant attention in large-scale energy storage. However, their practical application is hindered by zinc anode degradation, primarily dendrite growth and corrosion, which compromise battery performance and lifespan. Herein, we present an aluminum-doped silica (Al-SiO 2) aerogel coating layer to address these issues. The aluminum-doped silica aerogel coating layer offers improved hydrophilicity and zinc ion adsorption capabilities because of its porous structure, high surface area, and functional groups. By facilitating uniform zinc ion deposition and providing a physical barrier against corrosion, the Al-SiO 2 aerogel coating layer significantly mitigates dendrite formation and extends the electrochemical stability and operational lifespan of aqueous rechargeable zinc-metal-based batteries. Symmetric cell tests reveal that zinc anodes coated with Al-SiO 2 can achieve stable cycling over 3000 h, indicating exceptional reversibility and rate performance, much better than that of the bare Zn anode. Furthermore, the Al-SiO 2 aerogel-coated zinc anode coupled with MnO 2 cathode forms a stable rechargeable full battery. This work contributes to the body of knowledge on advanced materials for energy storage, highlighting the potential of aerogel coatings as a scalable and effective solution for improving the performance and durability of zinc metal anode for aqueous rechargeable zinc-metal-based batteries. [ABSTRACT FROM AUTHOR]

[Display omitted] • Stable MXene protective layer is planted on the surface of the zinc anode through a high-speed rotating wire brush. • The planted MXene layer brings a unique uniform electric field effect. • Zinc anode protected by planting MXene layer has better nucleation ability. • A high proportion of (0 0 2) crystal planes also inhibits dendrite formation. Aqueous zinc-ion batteries have good application prospects in large-scale energy storage, but severe dendrite behavior hinders their development. This article reports a method of planting MXene on the surface of zinc foil, that is, while mechanically polishing with a high-speed rotating wire brush, MXene solution is added dropwise, and MXene is anchored on the surface of the zinc foil with the help of a certain pressure. The MXene layer under this preparation method is stronger than the traditional self-assembled MXene layer. The MXene layer therefore acts as a physical barrier, protecting the underlying active zinc from damage. At the same time, the good hydrophilicity of the planted MXene layer reduces the concentration gradient of the interfacial electrolyte and redistributes the zinc ion flux. The unique electric field effect of MXene reduces the desolvation energy barrier, improves the transfer kinetics of Zn ions, and promotes the deposition of zinc ions in the (0 0 2) crystal plane. Experimental results show that the symmetrical battery prepared by this method can cycle stably for more than 1000 h at 0.8 mA cm−2, while its Zn\\Cu asymmetric battery exhibits cycle stability of more than 700 times at 0.5 mA cm−2. While maintaining a high Coulombic efficiency of over 99 %. Full cells assembled from zinc foil anodes and VO 2 cathodes protected by a planted MXene layer also demonstrate higher capacity advantages. Therefore, this more stable MXene layer provides a direction for the practical application of zinc metal anodes. [ABSTRACT FROM AUTHOR]

Aqueous zinc metal batteries (AZMBs) are deemed a promising technology for electrochemical energy storage due to their high safety, low cost, and high energy density. However, AZMBs still suffer from severe side reactions, including Zn dendrite formation and intrinsic hydrogen evolution reaction. In contrast to the solid‐electrolyte interphase (SEI) layer that stabilizes Li/Na/K metal anodes in organic electrolytes, it is difficult to form an SEI layer on the Zn surface because of the difficulty in decomposing the salt anions within the narrow electrochemical potential window of water. A team from the University of Adelaide reports a novel pure or hybrid electrolyte with H2O by using dimethyl methylphosphonate (DMMP) as solvent or co‐solvent to construct a uniform and stable phosphate‐based SEI layer (ZnP2O6 and Zn3(PO4)2). As a result, high Coulombic efficiencies and improved capacity retentions are obtained. [ABSTRACT FROM AUTHOR]

[Display omitted] • Porous nano-HfO 2 coating is used to protect zinc anode in zinc ion battery. • HfO 2 layer is prepared by a facile coating strategy. • Coated zinc anode shows good hydrophilia and surface wettability. • Coated zinc anode significantly inhibits formation of zinc dendrite. • Coated zinc anode exhibits excellent electrochemical performance. In aqueous zinc-ion batteries, metallic zinc is widely used as an anode because of its non-toxicity, environmental benignity, low cost, high abundance and theoretical capacity. However, growth of zinc dendrites, corrosion of zinc anode, passivation, and occurrence of side reactions during continuous charge-discharge cycling hinder development of zinc-ion batteries. In this study, a simple strategy involving application of a HfO 2 coating was used to guide uniform deposition of Zn2+ to suppress formation of zinc dendrites. The HfO 2 -coated zinc anode improves electrochemical performance compared with bare Zn anode. Therefore, for zinc-zinc symmetric cells, zinc anode with HfO 2 coating (48 mV) shows lower voltage hysteresis than that of bare Zn anode (63 mV) at a current density of 0.4 mA cm−2. Moreover, cell with HfO 2 coating also shows good cycling performance in Zn-MnO 2 full cells. At a constant current density of 1.0 A g−1, discharge capacity of bare Zn-MnO 2 full cell is only 37.9 mAh g−1 after 500 cycles, while that of Zn@HfO 2 -MnO 2 full cell is up to 78.3 mAh g−1. This good electrochemical performance may be the result of confinement effect and reduction of side reactions. Overall, a simple and beneficial strategy for future development of rechargeable aqueous zinc-ion batteries is provided. [ABSTRACT FROM AUTHOR]

Rechargeable nickel-zinc battery is regarded as a prospective choice for next-generation energy storage device due to its good safety, environmental friendliness and high energy density. However, zinc anode inevitably suffers from uncontrollable growth of zinc dendrites and the dissolution of zinc metal in high-concentration alkaline electrolytes, resulting in poor cycle stability and severely hampering the widespread applications of nickel-zinc batteries. Herein, a unique zinc anode with artificial solid electrolyte interface (ASEI) is facilely constructed via the rolling-tearing of tin and zinc foils and subsequent surface-based chemical reaction in a lead salt solution. The as-prepared ASEI composed of lead film has an efficient protective effect on preventing the dissolution of zinc anode. Meanwhile, the lead element and residual tin can not only enhance hydrogen evolution over-potential of zinc anode but affect the zinc growth mechanism. As a consequence, an excellent cyclic performances upto 100 cycles (capacity retention: 90%) with high reversible capacities are achieved for the zinc anode with AESI. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous Zn-based batteries are one of the most promising large-scale energy storage devices, benefiting from their eco-friendliness, low cost, high power/energy densities, and safety advantages without using flammable and poisonous organic liquid electrolytes. However, various challenges, such as infinite volume change and growth of dendrites during the electrostripping/electroplating process, lead to low cycling stability (cell shorting) and hinders the application of Zn-based batteries. Herein, a facile and effective approach to reduce graphene oxide (GO) spontaneously by zinc metal is developed and subsequently, the reduced graphene oxide (rGO) is self-assembled to create a layer-by-layer film on the Zn foil surface. This self-assembled, layered rGO on a Zn surface provides a large electroactive area and a soft substrate for Zn electrodeposition, which significantly mitigates Zn dendritic growth by eliminating its driving force. Compared with bare Zn, this composite anode exhibits much lower overpotential (~20 mV at 1 mA cm−2) and excellent long-life cyclability. A full-device with active carbon demonstrates good rate capacity and superior cycling stability. This well-designed anode also provides a useful solution and the possibility of constructing a dendrite-free advanced zinc anode. This is very important to all the zinc-based batteries for grid-scale storage. Unlabelled Image • A zinc metal anode coated by layered reduced oxide graphene is synthesized. • The approach presented in this work is a spontaneous and self-assembly process. • The reduced oxide graphene coating layer reduces polarization of anodes. • The reduced oxide graphene effectively suppresses the Zn dendrites formation. • This hybrid anode exhibits improved long-term cycling abilityin aqueous battery. [ABSTRACT FROM AUTHOR]

Zinc metal anodes offer low-cost and safe options for energy storage. However, the corrosion and dendritic growth limit battery longevity. In this study, a trace amount of 6-bromo-1 H-benzimidazole (BHB) is introduced as an electrolyte additive. Experimental and theoretical results demonstrate that BHB molecules adsorb on the zinc anode, suppressing corrosion, secondary reactions, and dendritic growth. BHB demonstrates exceptional corrosion inhibition (99.1%). BHB enables stable cycling of zinc anode for over 1150 h at 5 mA cm−2 and exhibits excellent zinc anode reversibility in Zn||Cu half-cells (CE=99.24%). This research provides an encouraging pathway for zinc anode electrolyte additives. [Display omitted] • BHB can significantly inhibit Zn corrosion and Zn dendrites in ZnSO 4 electrolyte. • The corrosion inhibition efficiency of BHB on zinc electrode can reach 99.1%. • Ultra-trace amounts of BHB promote uniform plating/stripping behavior of zinc. • BHB molecules adsorb on the surface of the Zn anode through a "catalytic-like effect". [ABSTRACT FROM AUTHOR]

Radially tinned copper nanowire zinc-loaded substrates were constructed on copper wire braid by means of directional nanosized growth and chemical in-situ tinning, and the integrated flexible device with antifreeze hydrogel has good low-temperature cycling stability and excellent resistance to external forces. [Display omitted] • The Cu-Sn NWs was made by chemical tin-plating combined with directional growth. • The Cu-Sn NWs mesh can attain uniform deposition of Zn2+ and inhibit dendrite growth. • The flexible ZIHCs show excellent good electrochemical property in cold environment. The aqueous zinc-ion hybrid capacitors (ZIHCs) have promising applications for large-scale energy storage due to high safety and low cost. However, the ZIHCs suffer from the poor cycling performance and the inability of the device to operate at freezing point. Herein, we designed an integrated device architecture consisting of a copper-tin nanowires (Cu-Sn NWs) array loaded zinc substrate with 3D pro-zinc channels assembled in-situ with a freeze-resistant electrolyte to realize flexible ZIHCs based on a dendrite free zinc anode. The Cu-Sn NWs with extremely low zinc nucleation overpotential induce uniform zinc deposition by homogenizing the electric field, while the resulting 3D nanowire array scaffold with ample internal space buffers the volume changes during the stripping/plating process. As-fabricated Zn-loaded substrate shows an extremely low voltage polarization of 23 mV and the outstanding ability to stably stripping/plating for 1200 h at 5 mA cm−1. Furthermore, the as-assembled flexible ZIHC is outstanding cycling performance (nearly 85.5% capacitance retention after 10,000 cycles at –20 °C) by in-situ polymerization of anti-freeze acrylamide-based composite hydrogel electrolyte on the zinc-loaded substrate. The strategy helps to stimulate the application of high-performance dendrite-free flexible energy-storage devices in cold environment. [ABSTRACT FROM AUTHOR]

[Display omitted] • DMAC is employed as a water dragger in low-concentration ZnSO 4 electrolytes. • DMAC suppresses the Zn2+–H 2 O solvation and facilitates the Zn2+-SO 4 2- coordination. • The Zn//Cu cell achieves a CE at 99.5% over 200 cycles with DMAC. • The Zn//MnO 2 full cell retains 81% of its initial capacity after 2000 cycles. Low-cost and high-safety aqueous zinc batteries are promising for large-scale energy storage applications. However, the actual performance of aqueous zinc batteries is hampered by the irreversibility of the zinc metal anode originating from the dendrite growth and side reactions, which are associated closely with the hydrated solvation sheath of Zn2+ ions in aqueous electrolytes. Here, dimethylacetamide is employed as a water dragger agent in low-concentration ZnSO 4 electrolytes to reshape the solvation structure of Zn2+ ions. Theoretical calculations and experimental investigations reveal that a low fractional addition of dimethylacetamide in aqueous ZnSO 4 electrolytes performs strong interactions with water molecules and Zn2+ ions, which inhibits hydrated Zn2+–H 2 O solvation, facilitates Zn2+-SO 4 2- association and captures free water molecules via H-bonds formation. The coulombic efficiency of Zn plating/stripping is improved from 94.3% to 98.1% and can be stabilized at 99.5% over 200 cycles with the hybrid electrolyte. The cycle lifespan of the Zn symmetric cell is prolonged over 1000 h at 1 mA cm−2 and over 450 h at 5 mA cm−2 with the dimethylacetamide -hybrid electrolyte, which are over fourfold higher than that of the pristine ZnSO 4 electrolyte. Moreover, when the designed electrolyte is incorporated in full cells, the Zn-MnO 2 cell exhibits an improved rate performance and an excellent long-term cyclability with a capacity-retention rate of 81% over 2,000 cycles at 1 A g−1. This work provides a feasible strategy for the development of highly stable aqueous zinc batteries. [ABSTRACT FROM AUTHOR]

Although aqueous zinc-ion batteries have been widely investigated as promising energy storage devices, the side effect of irreversible dendritic growth on cycling stability still exists to impede their practical applications. In this work, the porous rigid-flexible polymer composite membrane is successfully constructed by coupling rigid polymers of intrinsic microporosity (PIMs) with highly flexible polyvinylidene fluoride (PVDF). The afforded PVDF-PIM (P-PIM) membranes present various morphologies according to the different rigidity of PIMs. As a protective layer of zinc (Zn) anode, the PVDF-PIM-1 (P-PIM-1) membrane with a unique "sea-islands" morphology exhibits excellent electrochemical performances. The rigid island-region consists mainly of porous PIM-1, which is enriched with Zn2+ transport channels to enable fast reaction kinetics, and the flexible sea-region has a good dynamic adaptive capability. After coating P-PIM-1 membrane on Zn anode, the symmetric battery could retain 99.6% Coulombic efficiency (CE) after 500 plating/stripping cycles at a current density of 4 mA cm−2. The assembling P-PIM-1@Zn//NH 4 V 4 O 10 full battery delivers an ultra-long life of 14500 cycles and exceptional capacity retention of 113 mAh g−1 at 10 A g−1. The porous rigid-flexible interface provides a new approach for stable Zn anode. [Display omitted] • A polymer film with "sea-islands" morphology is used to prevent zinc dendrites. • The rigid island-phase of porous PIM is enriched with Zn2+ transport channels. • The flexible sea-phase of PVDF has a good dynamic adaptive capability. • The long lifespan of 2000 h at 0.5 mA cm−2 for modified Zn//Zn battery is achieved. • The full battery delivers an ultra-long life of 14500 cycles at 10 A g−1. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel WiDES electrolyte jointly suppresses cathode dissolution and Zn dendrites. • ChCl cosalt curbs water's activity in bulk electrolyte and Zn2+ solvation sheaths. • V 2 O 5 ·0.75H 2 O cathode keeps ∼292 mAh/g over 100 cycles at a harsh 50 mA g−1. • ZMA cycles up to 1600 h at a harsh rate of 0.2 mA cm−2 without dendrite formation. Aqueous Zn metal batteries (ZMBs) are promising to provide high energy density and inherent safety at a low cost, which is a candidate for large-scale energy storage. However, the cycle life of ZMBs is challenged by the cathode dissolution and irreversible plating/stripping of Zn metal anode (ZMA). Herein, we report a novel deep eutectic solvent electrolyte, 30 m ZnCl 2 + 15 m C 5 H 14 ClNO (choline chloride, ChCl), where ChCl restrains water's activity in both the bulk electrolyte and the Zn2+ solvation sheaths by coordinating with Zn2+. The presence of ChCl mitigates the cathode dissolution problem and eliminates the zinc dendrites of ZMBs. With this electrolyte, the vanadium oxide cathode, V 2 O 5 ·0.41H 2 O, maintains a capacity of ∼305 mAh g−1 over 100 cycles at a harsh current density of 50 mA g−1 and ∼180 mAh g−1 over 1500 cycles at 500 mA g−1; the ZMA can be cycled up to 1600 h at a harsh current density of 0.2 mA cm−2, 950 h higher than 30 m ZnCl 2 , without dendrite formation. This study highlights the function of ChCl as a co-salt for ZnCl 2 to facilitate high performance of ZMBs. [ABSTRACT FROM AUTHOR]

A hybrid aqueous rechargeable battery with Na 3 V 2 (PO 4 ) 3 as cathode and metal Zn as anode has been proposed. Na 3 V 2 (PO 4 ) 3 is co-incorporated by carbon and reduced graphene oxide. The battery delivers a capacity of 92 mAh g −1 at a current density of 50 mA g −1 with a high and flat operating voltage of 1.42 V. It exhibits a capacity of 60 mAh g −1 at a high current density of 2000 mA g −1 , indicative of excellent rate capability. Such inexpensive and safe battery shows an energy density as high as 112 Wh kg −1 , demonstrating that it is potential for future application in large-scale energy storage. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous zinc ion batteries have attracted significant attention because of their non-toxicity, high theoretical capacity, and low cost. However, many challenges regarding zinc anodes have hindered the development of zinc ion batteries, such as the growth of zinc dendrites, passivation and hydrogen evolution. In this study, a simple strategy based on porous rutile nano-TiO 2 coating was used to guide uniform deposition of zinc ions to inhibit the formation of zinc dendrite. The TiO 2 coated zinc anode shows excellent electrochemical performance. Therefore, for Zn Zn symmetric cell, the zinc anode protected by TiO 2 coating shows reduced voltage hysteresis (50 mV at 0.4 mA cm−2). Moreover, for Zn-MnO 2 full cell, the cell with TiO 2 coating also shows excellent cycling performance. The discharge capacity of Zn-MnO 2 full cell is only 27.69 mAh g−1 after 500 cycles, while discharge capacity of Zn@TiO 2 -MnO 2 full cell is up to 89.14 mAh g−1. This excellent electrochemical performance may be attributed to improved wettability of TiO 2 coated zinc anode, the uniform deposition of Zn2+ and reduction of Zn dendrites. Overall, this study provides a simple and beneficial strategy for future development of rechargeable aqueous zinc ion batteries. • Rutile nano-TiO 2 coating with uniform porous structure is used as protection layer for zinc anode. • Rutile nano-TiO 2 layer is coated on zinc anode via a facile strategy. • Coated zinc anode exhibits good hydrophilicity. • Coated zinc anode greatly improves cycle performance of aqueous zinc ion battery. [ABSTRACT FROM AUTHOR]

• Highly flexible CNT scaffolds were prepared and firstly used to stabilize Zn anodes. • The CNT scaffold-stabilized Zn anodes displayed superior cycling stability. • Ultralong-life zinc-ion batteries/hybrid capacitors with Zn anodes were constructed. The merits of zinc metal anodes such as high chemical stability, low cost and ultrahigh volumetric capacity endow Zn based batteries/hybrid capacitors with great potential applications for electronic products. However, unstable stripping/plating of zinc anodes tends to cause the formation of protuberances/dendrites and side reactions such as water decomposition on anode surfaces, eventually leading to the failure of Zn based electrochemical energy storage devices. Herein, we report the fabrication of free-standing, highly flexible and conductive carbon nanotube (CNT)/paper scaffolds to stabilize zinc metal anodes. The free-standing CNT scaffolds only need to be placed between zinc anodes and separators when assembling zinc anode-based batteries/hybrid capacitors. On the surface of the zinc electrode, the scaffolds' porous skeleton mechanically regulates Zn2+ deposition sites and their conductive CNT networks maintain a stable electric field during Zn stripping/plating processes, thus retarding the formation of protuberances/dendrites and the occurrence of side reactions. The scaffold-stabilized zinc anodes displayed small polarization voltages, a long cycling life over 1800 h and superior capability for fast charging-discharging. In addition, benefiting from the high electrochemical stability and reversibility of the scaffold-stabilized zinc anodes, zinc-ion batteries/hybrid capacitors with ultralong cycle lives were successfully constructed. This work provides a scalable approach to stabilize zinc metal anodes for long-life zinc-ion batteries and zinc-ion hybrid capacitors. [ABSTRACT FROM AUTHOR]