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Rechargeable aqueous Zn metal batteries (RAZMBs) are considered as a competitive alternative to the next generation of energy storage system. However, the Zn stripping/plating reversibility is greatly limited by the dendrite growth and the side reactions on Zn anode. In virtue of the excellent protection and ion migration regulation effects, porous organic polymer artificial solid electrolyte interphases (POPASEIs) have attracted widespread attention in stabilizing Zn anode. This article summarizes the progress of Zn anode POPASEIs in recent years, divided into two categories according to the polymer matrix: porous polymer‐based POPASEIs and nonporous polymer‐based POPASEIs. The porous polymer‐based POPASEIs can be divided into porous coordination organic polymer (PCOOP)‐based and porous covalent organic polymers (PCVOP)‐based ASEIs according to the chemical structure, while nonporous polymer‐based POPASEIs can be divided into four types according to the pore‐forming strategies, including phase separation‐induced POPASEIs, template‐assisted POPASEIs, fiber‐formed POPASEIs, porous filler‐modified POPASEIs. In addition, the structural advantages, challenges, and perspectives of POPASEIs for Zn anode are also discussed to provide guidance for the further research and development of Zn anode ASEIs. [ABSTRACT FROM AUTHOR]

K‐metal batteries have become one of the promising candidates for the large‐scale energy storage owing to the virtually inexhaustible and widely potassium resources. The uneven K+ deposition and dendrite growth on the anode causes the batteries prematurely failure to limit the further application. An integrated K‐metal anode is constructed by cold‐rolling K metal with a potassiphilic porous interconnected mediator. Based on the experimental results and theoretical calculations, it demonstrates that the potassiphilic porous interconnected mediator boosts the mass transportation of K‐metal anode by the K affinity enhancement, which decreases the concentration polarization and makes a dendrite‐free K‐metal anode interface. The interconnected porous structure mitigates the internal stress generated during repetitive deposition/stripping, enabling minimized the generation of electrode collapse. As a result, a durable K‐metal anode with excellent cycling ability of exceed 1, 000 h at 1 mA cm−2/1 mAh cm−2 and lower polarization voltage in carbonate electrolyte is obtained. This proposed integrated anode with fast K+ kinetics fabricated by a repeated cold rolling and folding process provides a new avenue for constructing a high‐performance dendrites‐free anode for K‐metal batteries. [ABSTRACT FROM AUTHOR]

Aqueous zinc ion batteries (AZIBs) are promising electrochemical energy storage devices due to their high theoretical specific capacity, low cost, and environmental friendliness. However, uncontrolled dendrite growth poses a serious threat to the reversibility of Zn plating/stripping, which impacts the stability of batteries. Therefore, controlling the disordered dendrite growth remains a considerable challenge in the development of AZIBs. Herein, a ZIF-8-derived ZnO/C/N composite (ZOCC) interface layer was constructed on the surface of the Zn anode. The homogeneous distribution of zincophilic ZnO and the N element in the ZOCC facilitates directional Zn deposition on the (002) crystal plane. Moreover, the conductive skeleton with a microporous structure accelerates Zn2+ transport kinetics, resulting in a reduction in polarization. As a result, the stability and electrochemical properties of AZIBs are improved. Specifically, the ZOCC@Zn symmetric cell sustains over 1150 h at 0.5 mA cm−2 with 0.25 mA h cm−2, while the ZOCC@Zn half-cell achieves an outstanding Coulombic efficiency of 99.79% over 2000 cycles. This work provides a simple and effective strategy for improving the lifespan of AZIBs. [ABSTRACT FROM AUTHOR]

Dendritic deposition and side reactions have been long‐standing interfacial challenges of Zn anode, which have prevented the development of practical aqueous zinc‐based batteries. Herein, an oxygen vacancy‐rich CeO2 aerogel (VAG‐Ce) interface layer that simultaneously integrates Zn2+ selectivity, porosity, and is lightweight is reported as a new strategy to achieve dendrite‐free and corrosion‐free Zn anodes. The well‐defined and uniform nanochannels of VAG‐Ce can act as ion sieves that redistribute Zn2+ at the Zn anode surface by regulating Zn2+ flux, leading to uniform Zn deposition and significantly suppressing dendrite growth. Importantly, the abundant oxygen vacancies exposed on VAG‐Ce surface can strongly capture SO42−, forming a negatively charged layer that can attract Zn2+ and accelerate the Zn2+ migration kinetics, while the subsequent repulsion of additional anions can effectively suppress the generation of (Zn4SO4(OH)6·xH2O) byproducts, thereby realizing very stable Zn anodes. Consequently, VAG‐Ce modified Zn anode (VAG‐Ce@Zn) enables a long‐term lifespan over 4000 h at 4 mA cm−2 and a record‐high cycle life of 1200 h is achieved under an ultrahigh 85% Zn utilization at 8 mA cm−2, which enables excellent capacity retention and cycling performance of VAG@Zn/MnO2 cells. This work contributes an innovative design concept by introducing oxygen vacancy‐rich aerogels and provides a new horizon for stabilizing Zn anode for large‐scale energy storage. [ABSTRACT FROM AUTHOR]

Zinc‐based energy storage has lately gained popularity due to natural abundance, operational safety, high energy density. Unfortunately, dendrite growth is a common and intractable issue faced in existing zinc‐ion batteries to shorten cycle lifespan/stability. This review summarizes recent progress in assembly component (e. g. anode, electrolyte, separator) engineering for dendrite‐free zinc‐ion batteries. First, diversiform strategies of Zn surface modification and Zn host design are presented to shield the fundamental adverse effect aroused by uneven zinc deposition on the anode. Then, subtle deployments of electrolyte constituents are illustrated to optimize the Zn2+ solvation structure for ultimate dendrite control and Coulombic efficiency elevation in aqueous systems and beyond (e. g. eutectic electrolytes). Furthermore, rational manipulation of advanced separators and the upgrade of zinc metal‐free Zn2+‐storage devices are briefly discussed to explore the dendrite‐free and high‐level Zn2+‐storage. Finally, challenges and perspectives are proposed to offer research inspirations toward safe, high‐efficiency and long‐lifespan zinc storage. [ABSTRACT FROM AUTHOR]

With the development of consumer electronic devices and electric vehicles, lithium‐ion batteries (LIBs) are vital components for high energy storage with great impact on our modern life. However, LIBs still cannot meet all the essential demands of rapidly growing new industries. In pursuance of higher energy requirement, metal batteries (MBs) are the next‐generation high‐energy‐density devices. Li/Na metals are considered as an ideal anode for high‐energy batteries due to extremely high theoretical specific capacity (3860 and 1165 mAh g−1 for Li and Na, respectively) and low electrochemical potential (−3.04 V for Li and −2.71 V for Na vs. standard hydrogen electrode). Unfortunately, uncontrolled dendrite growth, high reactivity, and infinite volume change induce severe safety concerns and poor cycle efficiency during their application. Consequently, MBs are far from commercialization stage. This Review represents a comprehensive overview of failure mechanism of lithium/sodium metal anode and its progress for rechargeable batteries through (i) electrolyte optimization, (ii) artificial solid‐electrolyte interphase (SEI) layer formation, and (iii) nanoengineering at materials level in current collector, anode, and host. The challenges in current MBs research and potential applications of lithium/sodium metal anodes are also outlined and summarized. [ABSTRACT FROM AUTHOR]

This review focuses on the Na wetting challenges and relevant strategies regarding stabilizing sodium-metal anodes in sodium-metal batteries (SMBs). The Na anode is the essential component of three key energy storage systems, including molten SMBs (i.e., intermediate-temperature Na-S and ZEBRA batteries), all-solid-state SMBs, and conventional SMBs using liquid electrolytes. We begin with a general description of issues encountered by different SMB systems and point out the common challenge in Na wetting. We detail the emerging strategies of improving Na wettability and stabilizing Na metal anodes for the three types of batteries, with the emphasis on discussing various types of tactics developed for SMBs using liquid electrolytes. We conclude with a discussion of the overlooked yet critical aspects (Na metal utilization, N/P ratio, critical current density, etc.) in the existing strategies for an individual battery system and propose promising areas (anolyte incorporation and catholyte modifications for lower-temperature molten SMBs, cell evaluation under practically relevant current density and areal capacity, etc.) that we believe to be the most urgent for further pursuit. Comprehensive investigations combining complementary post-mortem, in situ, and operando analyses to elucidate cell-level structure-performance relations are advocated. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous Zn‐ion batteries (ZIBs) are regarded as one of the most promising devices for the next‐generation energy storage system. However, the uncontrolled dendrite growth on Zn metal anodes and the side hydrogen evolution reaction, which has not yet been well considered, hinder the practical application of these batteries. Herein, a uniform and robust metallic Sb protective layer is designed based on the theoretic calculation and decorated on Zn plate via in situ replacement reaction. Compared with the bare Zn plate, the as‐prepared Zn@Sb electrode provides abundant zincophilic sites for Zn nucleation, and homogenizes the electric field around the Zn anode surface, both of which promote the uniform Zn deposition to achieve a dendrite‐free morphology. Moreover, the Gibbs free energy (∆GH) calculation and in situ characterization demonstrate that hydrogen evolution reaction can be effectively suppressed by the Sb layer. Consequently, Sb‐modified Zn anodes exhibit an ultralow voltage hysteresis of 34 mV and achieve excellent cycling stability over 1000 h with hydrogen‐ and dendrite‐free behaviors. This work provides a facile and effective strategy to suppress both hydrogen evolution reaction and dendrite growth. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries (AZIBs) are expected to be the next generation of energy storage devices, but severe dendrite growth hindering the large-scale application of AZIBs. In this paper, a citric acid (CA) etching method is used to optimize zinc anode, which is referred to as CA-Zn. After citric acid etching, the zinc anode surface was exposed to a high proportion of (002) crystal planes, and the stable (002) crystal planes inhibited the formation of zinc surface by-products. Moreover, acid etching etched micro-grooves on the zinc surface, which increased the electrochemically active surface area of the zinc anode. And the plating/stripping kinetics of Zn/Zn2+ was enhanced. Consequently, the CA-Zn symmetric battery has a stable cycle of 550 h at 1 mA cm−2 and 1 mAh cm−2. AZIBs composed of CA-Zn and activated carbon showed a specific capacity of up to 83.5 mAhg−1 and CE close to 100% during cycling 1500 cycles at a current density of 0.5 A g−1. This paper explores a new method to protect zinc metal by citric acid etching, which provides a new idea for future research. [Display omitted] • A simple method of etching zinc anodes surface in citric acid • More nucleation sites were constructed on the zinc surface. • The zinc anodes with more (002) crystal planes exposure were obtained. • The zinc anodes etched with citric acid have excellent electrochemical properties. [ABSTRACT FROM AUTHOR]

Rechargeable sodium batteries are a promising technology for low‐cost energy storage. However, the undesirable drawbacks originating from the use of glass fiber membrane separators have long been overlooked. A versatile grafting–filtering strategy was developed to controllably tune commercial polyolefin separators for sodium batteries. The as‐developed Janus separators contain a single–ion‐conducting polymer‐grafted side and a functional low‐dimensional material coated side. When employed in room‐temperature sodium–sulfur batteries, the poly(1‐[3‐(methacryloyloxy)propylsulfonyl]‐1‐(trifluoromethanesulfonyl)imide sodium)‐grafted side effectively enhances the electrolyte wettability, and inhibits polysulfide diffusion and sodium dendrite growth. Moreover, a titanium‐deficient nitrogen‐containing MXene‐coated side electrocatalytically improved the polysulfide conversion kinetics. The as‐developed batteries demonstrate high capacity and extended cycling life with lean electrolyte loading. [ABSTRACT FROM AUTHOR]

Zn−Ni secondary battery is a promising candidate as next generation of energy storage battery. However, suffering from the poor cycle performance, its commercialization remains rather challenging. The severe dendrite growth of Zn anode and the rapid capacity decay caused by its uncontrollable dissolution and poor electronic conductivity of ZnO are the main factors. Herein, we report a novel Indium (In) doped ZnO/rGO anode material to inhibit ZnO dissolution through the generated C−O−Zn bond between ZnO and graphene. Meanwhile, the capacity decay decline due to the enhanced electronic conductivity of ZnO by the In doping and combination of graphene. As a result, In doped ZnO/rGO anode material delivers a high specific capacity of 643.4 mAh g−1 (coulombic efficiency 97.63 %) and remains 531.3 mAh g−1 after 125 cycles at 0.5 C, which are significantly higher than bare ZnO. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (AZIBs) have attracted increasing attention as a next‐generation energy storage system because of their inherent safety, high capacity, and cost effectiveness. However, the poor cycling durability and low coulombic efficiency of zinc anodes substantially restrict their further development, which should be attributed to the severe dendrite growth, shape change, surface passivation, self‐corrosion, and byproduct formation across the repeated plating/stripping processes. To address these critical issues, great efforts have been dedicated to the rational design of zinc anodes. In this review, different strategies for the performance improvement of zinc anodes are summarized as well as recent research that boosts their development. These methods include the surface modification, novel host‐anode development for zinc, electrolyte formulation, and separator design. Their respective advantages and defects are compared and discussed in detail. The challenges and further prospects in this field are also addressed. This work is designed to shed light on advanced zinc anode constructions for high‐performance AZIBs assembly. [ABSTRACT FROM AUTHOR]

Abstract Li-metal battery (LiMB) has received considerable attention as an alternative energy storage device to Li-ion battery in recent years. However, uncontrolled Li dendrite growth prevents the practical applications of LiMB. Herein, we report the use of concentrated electrolytes based on dual salts of lithium bis(fluorosulfonyl) imide (LiFSI) and lithium difluoro(oxalato) borate (LiODFB) to suppress Li dendrite growth. The compatibility of electrolyte and LiFePO 4 cathode was further verified by the long capacity retention and high rate performance of Li/LiFePO 4 battery. The superior electrochemical performance was attributed to the concentrated electrolyte, which could simultaneously suppress Li dendrite growth at the anode side and Aluminum (Al) current collector corrosion at the cathode side. This work provides new insights to develop high-performance LiMBs by carefully tailoring the multivariate composition of concentrated electrolyte. [ABSTRACT FROM AUTHOR]

Constructing carbon materials with ample active sites, reasonable defects, considerable capacity and durability are vital but still challenging for high energy K+ storage devices. Herein, a multi-pronged nanostructure enables superior K+ storage (high rate capability, long-term cycling performance, high areal capacity, ultrahigh energy density of 311.8 Wh kg−1) and self-regulating dendrite-free K plating, opening up new possibility for high-performance and stable potassium-based storage. [Display omitted] • The Tetramethylol Acetylenediurea (TA) derived versatile carbon was constructed. • Excellent cycling stability and a high areal capacity were achieved. • Self-regulated dendrite-free K plating was presented. • The full-cell battery with organic cathode delivered ultrahigh energy density. Reasonably constructed carbon-based electrodes are highly crucial for designing high-performance potassium-ion and potassium metal batteries (PIBs or PMBs). To this end, we developed a Tetramethylol Acetylenediurea derived versatile carbon with rational design of multi-pronged active sites, superior kinetics and robust stability via unique nanoengineering strategies. Specifically, in situ characterizations (e.g. , in-situ EIS and in-situ Raman) and theory calculations further unveiled the fundamentals of storage mechanisms. As a result, it delivered high rate capability, remarkable long-term cycling performance for over 2,400 cycles at 1 A/g, high areal capacity of 2.7 mAh cm−2 at a high mass loading of 8 mg cm−2 and low potassium nucleation overpotential (14.9 mV at 1 mA cm−2). Moreover, the potassium-ion full-cell battery pairing with an organic perylene-3,4,9,10-tetracarboxylic dianhydride cathode enabled ultrahigh energy density of 311.8 Wh kg−1, proving a representing advances in high-performance and stable potassium-based storage. [ABSTRACT FROM AUTHOR]

[Display omitted] • A Zn2+-complexed nanoporous polyelectrolytic interlayer is designed. • The self-assembled interlayer enabled highly reversible Zn metal anodes. • Cycling performance of Zn metal batteries is significantly improved. Aqueous zinc-ion batteries (AZIBs) based on Zn metal anodes are promising candidates for next-generation energy storage due to their high performance, environmental friendliness, low cost, and high abundance. However, the excessive dendrite growth and continuous hydrogen evolution of Zn metal anodes in aqueous electrolytes severely deteriorate the electrochemical performance of AZIBs. Here, a highly stable Zn metal anode is designed by reconstructing its surface with a self-assembled nanoporous polyelectrolytic interlayer. This unique protective layer consisting of polyacrylic acid-zinc (PAAZn) nanospheres is highly hydrophilic and can act as a physical barrier to reduce the contact between Zn metal and water molecules, thus suppressing hydrogen evolution and Zn corrosion. Meanwhile, the unique nanostructures and chemical compositions of the PAAZn interlayer ensure fast Zn plating/stripping kinetics and facilitate the homogeneous growth of Zn deposits by redistributing Zn ion flux and local electric field at Zn/electrolyte interfaces. Therefore, symmetric cells based on the PAAZn-modified Zn metal anode (PAAZn@Zn) exhibited a significantly prolonged cycle life of 2,850 h and low voltage hysteresis. This work reports a uniquely designed nanoporous polyelectrolytic interlayer for highly reversible Zn metal anodes and provides a new strategy to enhance the electrochemical performance of AZIBs. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion battery, cycle performance, dendrite growth, eutectic electrolyte, Zn anode Keywords: aqueous zinc-ion battery; cycle performance; dendrite growth; eutectic electrolyte; Zn anode EN aqueous zinc-ion battery cycle performance dendrite growth eutectic electrolyte Zn anode 1 1 1 04/10/23 20230406 NES 230406 Diversiform engineering strategies of each assembly components are presented to tackle the intractable dendrite growth issue faced in existing zinc-ion batteries toward safe, high-efficiency and long-lifespan energy storage. Frontispiece: Dendrite-Free Engineering toward Efficient Zinc Storage: Recent Progress and Future Perspectives. [Extracted from the article]

Rechargeable aqueous zinc-ion batteries are attractive candidates as energy storage technology, but the uncontrollable Zn dendrite formation and low stripping/plating coulombic efficiency when using bare Zn metal foil as anode have severely limit the battery reliability and energy density. Thus, to develop a more robust ZIB anode with lower extent of dendrite growth, Zn–Al alloy is proposed in this work. The passivating Al 2 O 3 shell formed on the Al phase can provide two key functions; (1) selective electrochemical stripping of Zn due to electrochemically inert Al 2 O 3 , and (2) guiding the electrodeposition of Zn on the available Zn sites. The as-prepared Zn–Al alloy anode is able to outperform the bare Zn anode as bare Zn anode shows signs of short circuit after cycling. When paired with V 6 O 13 cathode, the Zn–Al//V 6 O 13 cell delivers enhanced rate performance and a nearly 95% capacity retention after 1000 cycles at 3 A g−1, with a specific capacity of 280 mA h g−1. The strategy demonstrated that Zn–Al alloy is suitable for aqueous zinc-ion batteries due to its low corrosion rate, low dendrite formation, low corrosion current, and high capacity retention. [Display omitted] • Metallurgical smelting method is employed to prepare Zn–Al alloy anode. • Zn–Al alloy anode achieves uniform Zn deposition and suppress the Zn passivation. • Zn–Al//V 6 O 13 cell delivers enhanced rate performance and good capacity retention. [ABSTRACT FROM AUTHOR]

In spite of the strong relevance of electrochemical energy conversion and storage, the atomistic modeling of structures and processes in electrochemical systems from first principles is hampered by severe problems. Among others, these problems are associated with the theoretical description of the electrode potential, the characterization of interfaces, the proper treatment of liquid electrolytes, changes in the bulk structure of battery electrodes, and limitations of the functionals used in first-principles electronic structure calculations. We will illustrate these obstacles, but also indicate strategies to overcome them. [ABSTRACT FROM AUTHOR]

To build a sustainable society, the governments and industries are replacing fossil fuels for clean energy technologies, which produce electricity intermittently and need efficient energy storage systems. Thus, Na-ion batteries are the most attractive technologies as sodium is the most cost effective, earth-abundant and environment-friendly alternative. However, the design of anodic materials with reversible Na-ion (de)insertion represents one of the principal issues to improve in anodic electrodes. Typical ex-situ microscopy techniques may not correctly reveal the actual phenomena occurring at working conditions in NIB anodes, limiting the fundamental understanding of the anode performance. Therefore, monitoring in real-time the structural and chemical transformation of Na-ion anodes during (dis)charge cycling is a paramount objective. The development of operando methodologies, such as transmission electron, atomic force and light microscopies, has allowed to follow: phase transformation, growth of solid electrolyte interface and sodium dendrites. The progress on operando microscopy techniques indicates a promising route to acquire meaningful information to draw the path to improve the efficiency and sustainability of Na-ion anodes. This review emphasizes the need of operando techniques for NIBs, their state-of-the-art findings, cohesive understanding of various insertion, alloying and conversion reactions, and unanswered questions providing direction to futuristic research. • Operando Microscopy Techniques allow a deep comprehension of some anodic processes. • Operando TEM microscopy monitors phase transformation in Na-ion anodes. • Operando LM microscopy disclose the growth mechanisms of Na dendrites. • Operando AFM microscopy revels the SEI formation and growth of Na-ion anodes. [ABSTRACT FROM AUTHOR]