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[Display omitted] • Trace additive effectively extends the cycle life of ZIBs. • The adsorbed NTA molecules reduce the de-solvation energy barrier. • NTA molecules provide a buffer layer to retard dendrite growth. Aqueous Zn-ion batteries (AZIBs) have attracted widespread attention due to their intrinsic safety, cost-effectiveness. However, active H 2 O in the solvated ions [Zn(H 2 O) 6 ]2+ continuously migrate to the Zn surface to trigger hydrogen evolution reaction (HER) and accelerate Zn corrosion. Herein, Zn dendrites and the related by-products have been successfully inhibited by using trace amounts of Nitrilotriacetic acid (NTA). Theoretical research indicates that two carboxyl groups of NTA molecule strongly anchored on the Zn surface and exposed another carboxyl group outside. Due to the violent interaction of carboxyl groups of NTA with H 2 O, the de-solvation energy barrier of solvated Zn2+ ([Zn(H 2 O) 6 ]2+) on the Zn surface was obviously decreased, inhibit the active water splitting. Meanwhile, the preferential adsorption of NTA on the Zn surface increases the thickness of electric double layer EDL and provides a buffer layer to hinder the dendrite growth. Using 0.04 M NTA as additives in 2.0 M ZnSO 4 electrolyte, the cycling lifespan of both Zn||Zn symmetric and Zn||MnO 2 full cells is markedly prolonged. This study provides certain perspectives for trace amounts of electrolyte additives to satisfy the demand of long-cycle life AZIBs. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐ion batteries are promising for large‐scale energy storage due to low cost and high safety. However, aqueous electrolyte induces severe side reactions at Zn anode, especially hydrogen evolution reaction (HER). Herein, it is first revealed that the freshly nucleated‐Zn (FN‐Zn) atoms during plating process show higher reactivity and stronger adsorption of proton than metallic Zn anode by X‐ray absorption near edge structure (XANES) and corresponding extended X‐ray absorption fine structure (EXAFS), and density functional theory simulations, promoting the decomposition of H2O. Then, a universal and effective capping effect strategy is proposed to alleviate HER by electrostatically shielding FN‐Zn activity. Specifically, sodium benzenesulfonate (SBS) is selected as a typical example by screening and comparing a series of electrolyte additives, in which sulfonate group with high coordination energy can be preferentially capped on FN‐Zn to reduce its reactivity. Consequently, the symmetrical cell with SBS not only generates negligible amounts of H2 by in situ electrochemical‐gas chromatography but also can be up to 2550 h at 1 mA cm−2. More importantly, the capping effect on HER‐free Zn anode is verified by coin full cells exhibiting capacity retention of≈87.1% after 1000 cycles and large‐area (4 × 6 cm2) pouch cells with desired performance. [ABSTRACT FROM AUTHOR]

The practical application of aqueous zinc ion batteries (AZIBs) is impeded by the instability of the Zn anode|electrolyte interface, including dendrite growth, hydrogen evolution reaction (HER), and corrosion. Herein, the periodical micro‐nano structure is constructed on the surface of Zn anode through picosecond laser lithography (PLL) technology. This micro‐nano surface structure is conductive to obtain hydrophobicity for diminishing direct contact between the electrolyte and Zn anode, enhancing the corrosion resistance of the Zn anode. Simultaneously, the low surface energy and reconstructed electric field are achieved through laser‐induced texture microstructure, leading to the oriented Zn2+ deposition along the (002) plane. As a result, the lower electrochemical polarization and long cycling stability of 1400 h for Zn||Zn symmetric cell is achieved at 4 mA cm−2 and 2 mAh cm−2. The average coulombic efficiency (CE) of the Zn||Cu cell is enhanced to 99.83% at 2 mA cm−2, while the Zn||MnO2 cell delivers a capacity retention of 68.7% after 600 cycles at 1 A g−1. Consequently, the advantages of micro‐nano structure can highlight the importance of surface structure design for the development of stable Zn anode. [ABSTRACT FROM AUTHOR]

Effective selective recycling of spent lithium‐ion batteries (S‐LIBs) and giving recycled products a "second life" are crucial for advancing energy supply circularity, environmental and economic sustainability development. However, separating metal compounds with similar charge differences requires substantial energy, water, and chemical inputs. Herein, an innovative strategy is present for selective recycling S‐LIBs by photoexcitation inspired by the Hard Soft Acid Base (HSAB) principle. Theoretical calculations and experimental results show that photoexcitation drives charge transfer and modulates subtle charge density differences among metal components, thereby enhancing their solubility disparity and facilitating metal separation. Remarkably, the photoexcitation‐induced metal separation factor reaches 46900 and the metal recovery efficiency approaches 100%, representing a significant improvement over non‐photoexcitation separation with a separation factor of non‐photoexcitation of merely 2.7. Through techno‐economic analysis, the viability of photoexcitation selective recycling technology has been confirmed as an eco‐friendly and economical approach for battery recycling. Furthermore, high‐value reuse of recovered Mn components is implemented. The Recycled Mn components are treated by calcination to obtain porous, defect‐rich Mn2O3, which showed a specific capacity of 613 mAh g−1 at 0.1 A g−1) in aqueous Zn‐ion batteries (AZIBs). This work provides fresh insight into recycling S‐LIBs and moving toward more sustainable storage technologies. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐ion batteries (AZIBs) are promising for the next‐generation large‐scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P‐CD) to construct quasi‐single ion conductor for coating and protecting Zn anodes. The P‐CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host–guest interactions and hydrogen bonds, forming a quasi‐single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P‐CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm−2 with 10 mAh cm−2. Importantly, the Zn//K1.1V3O8 (KVO) full‐cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5 % after 1000 cycles at 10 A g−1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid‐electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs. [ABSTRACT FROM AUTHOR]

In the field of energy technologies, self‐charging batteries are receiving extensive attention. However, the existing technologies are highly dependent on the available sources of O2, have long self‐charging duration, and have complex architectures. Herein, a novel ultrafast chemical self‐charging Zn‐quinhydrone polymer gel (QPG) battery, composed of acid/base free quinhydrone as a cathode material is reported. The prepared Zn–QPG battery exhibits a specific capacity of 209.7 mAh g−1 at 10C rate and maintains 86.4% of the initial discharge capacity even after 3000 cycles with a high coulombic efficiency of 99.4%. The aqueous amphiphilic block co‐polymer‐driven selective oxidation of hydroquinone (HQ) to benzoquinone (BQ) compels the chemical self‐charging feature wherein the device attains ≈1.1 V within ten minutes of complete discharge. The chemical self‐charging generated a high specific capacity of 197.8 mAh g−1 at 10C rate with a capacity retention of 91.2% after 100 cycles. Moreover, a flexible Zn–QPG battery also demonstrates excellent rechargeability and power‐delivering ability even in a wrist‐bend geometry. This work paves the way to develop ultrafast energy storage systems, which are not dependent on an external power supply and broaden the horizon of aqueous zinc–organic batteries. [ABSTRACT FROM AUTHOR]

Polymers with redox activity are one type of promising candidates of cathode materials for aqueous Zn‐ion batteries due to their potential low‐cost, high safe, and renewable features. Unfortunately, suboptimal polymer electrode structure often results in unsatisfactory electrochemical performance. Herein, poly(1,8‐diaminonaphthalene)/active carbon composite electrodes are prepared via nanoconfined in situ electropolymerization within porous active carbon, which have ultrahigh specific surface area (1035.0 m2 g−1) and unique nano‐porous structure, thereby highly enhancing the utilization of the active site up to 91.6%. The as‐prepared cathodes deliver ultrahigh reversible capacity of 479.5 mAh g−1, ultrafast rate capability of up to 60 A g−1 and an ultralong life span of 50,000 cycles. Storage mechanism investigation indicates that the cathode material involves a bipolar‐type behavior. These encouraging results demonstrate that nanoconfined in situ electropolymerization in active carbon is a brand‐new strategy for the design of advanced polymer electrodes for high‐performance aqueous Zn‐organic batteries. [ABSTRACT FROM AUTHOR]

Mn‐based oxides are broadly prospected cathode materials for aqueous Zn‐ion batteries (AZIBs) due to their rich abundance, low cost, and plentiful valence states. However, the further development of Mn‐based oxides is severely restricted by the dissolution of active materials and poor structural stability. Herein, hollow octahedral Pr6O11‐Mn2O3 (denoted as PrO‐MnO) heterostructures are developed through a facile metal–organic framework‐engaged templating approach, which realizes boosted Zn ion storage performance. Pr6O11 can not only effectively suppress the dissolution of Mn to stabilize Mn2O3 but also induce interfacial charge rearrangement and promote electron/ion transfer, contributing to the improved electrochemical activity and stability of PrO‐MnO. Moreover, the rationally designed hollow nanostructure offers sufficient active sites and facilitates the reaction kinetics. As expected, the PrO‐MnO cathode exhibits excellent rate and cycling performance with a high reversible capacity of 140.8 mAh g−1 after 2000 cycles at 1 A g−1, outperforming the Mn2O3 cathode. [ABSTRACT FROM AUTHOR]

Exploring cathode materials with excellent electrochemical performance is crucial for developing rechargeable aqueous zinc ion batteries (RAZIBs). Zinc hexacyanoferrate (ZnHCF), a promising candidate of cathode materials for RAZIBs, suffers from severe electrochemical instability issues. This work reports using low contents of alkaline metal cations as electrolyte additives to improve the cycle performance of ZnHCF. The cations with large sizes, particularly Cs+, changes the intercalation chemistry of ZnHCF in RAZIBs. During cycling, Cs+ cations co‐inserted into ZnHCF stabilize the host structure. Meanwhile, a stable phase of CsZn[Fe(CN)6] forms on the ZnHCF cathode, suppressing the loss of active materials through dissolution. ZnHCF gradually converts to an electrochemically inert Zn‐rich phase during long‐term cycling in aqueous electrolyte, leading to irreversible capacity loss. Introducing Cs+ in the electrolyte inhibits this conversion reaction, resulting in the extended lifespan. Owing to these advantages, the capacity retention rate of ZnHCF/Zn full batteries increases from the original 7.0 % to a high value of 54.6 % in the electrolyte containing 0.03 M of Cs2SO4 after 300 cycles at 0.25 A ⋅ g−1. This research provides an in‐depth understanding of the electrochemical behavior of ZnHCF in aqueous zinc electrolyte, beneficial for further optimizing ZnHCF and other metal hexacyanoferrates. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐ion batteries (AZIBs) are promising energy storage systems due to their low cost, excellent safety, and environmental friendliness. However, challenges like uncontrollable dendrite growth and side reactions during battery operation limit their commercialization. Addressing these issues requires regulating ion deposition behavior at the anode/electrolyte interface. The electrostatic shielding effect, which leverages the interplay between electric potential and ionic motion, provides a unique mechanism to inhibit zinc dendrites and side reactions effectively. Despite significant progress in understanding electrostatic shielding in AZIBs, a comprehensive summary of its effects is still lacking. This paper first reviews the primary challenges in AZIBs and then describes how the electrostatic shielding effect can optimize their performance. Existing strategies for achieving electrostatic shielding through anode structure optimization and electrolyte optimization‐are classified and analyzed. Finally, the review summarizes current electrostatic shielding strategies for stabilizing zinc anodes, identifies existing challenges, and discusses the future potential, and for this approach in AZIBs. [ABSTRACT FROM AUTHOR]

The zinc metal anodes are liable to experience detrimental dendrite growth and side reactions, thereby limiting the lifespan of aqueous Zn‐ion batteries. Here, a readily available supramolecule, dimethoxypillar[5]arene (DP[5]), is utilized as a shielding layer to stabilize the Zn anode by exploiting its zincophilicity derived from the ─OCH3 functional groups and its hydrophobicity from the hydrophobic backbone. The DP[5] shielding layer regulates the solvation sheath of Zn2+ and facilitates uniform zinc deposition. Swelling and dendrite formation are obviously suppressed in both the symmetric and full cells. The DP[5]‐Zn symmetrical cell cycles stably for 5500 h, and achieves a coulombic efficiency of 99.76% in a DP[5]‐Zn||Cu half‐cell after 2200 cycles. The DP[5]‐Zn||V2O5 full cell maintains 92.03% of initial capacity after 6000 cycles. Given the cost‐effective fabrication and environmental friendliness of DP[5] films, this material may pave the way for practical applications of zinc anodes. [ABSTRACT FROM AUTHOR]

Inspired by the desire to solve a series of problems such as the easy mottling and peeling of the physically attached artificial interfacial layer on the surface of Zn anode, ZnSiO 3 with a nanosheet morphology was constructed on the surface of Zn foil through the self-growth reaction. The ZnSiO 3 nano-interfacial layer effectively slices the surface of the Zn foil into individual microscopic interfacial layers, and this study provides a new perspective for the interfacial engineering of the protection of Zn anodes. [Display omitted] Among battery technologies, aqueous zinc ion batteries (AZIBs) have hit between the eyes in the next generation of extensive energy storage devices due to their outstanding superiority. The main problem that currently restricts the development of AZIBs is how to obtain stable Zn anodes. In this study, taking the improvement of a series of problems caused by the physically attached artificial interfacial layer on Zn anode as a starting point, a nanosheet morphology of ZnSiO 3 (denoted as ZnSi) is constructed by self-growth on Zn foil (Zn@ZnSi) by a simple hydrothermal reaction. The ZnSi nano-interfacial layer effectively slices the surface of the Zn foil into individual microscopic interfacial layers, constructing abundant pores. The nanosheets of Zn@ZnSi construct rich nanoscale Zn2+ transport channels, which provide higher electron and ion transport paths, thus achieving the effect of effectively homogenizing the electric field distribution and decreasing the local current density. Thanks to its inherent and structural properties, the Zn@ZnSi anode has a high specific capacity and good cycling stability compared with the Zn electrode. The lifetime of the Zn@ZnSi//Zn@ZnSi symmetric cell is much higher than that of the Zn//Zn symmetric cell at 1 mA cm−2. The capacity of the Zn@ZnSi//NH 4 V 4 O 10 full cell can still reach 98 mAh g−1 after 1000 cycles at 1 A/g. The low-cost and scalable synthesis of ZnSi nano-interfacial layer on Zn is expected to provide new perspectives on interfacial engineering for Zn anodic protection. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (ZIBs) present significant promises for next‐generation energy storage systems. However, challenges such as the zinc (Zn) dendrite formation and parasitic side reactions during Zn plating‐stripping hinder their development. Herein, an aloe vera (AV)‐based green and sustainable electrolyte is formulated to increase the electrochemical stability of the ZIBs, reducing the free water molecules, and decreasing the hydrogen evolution reaction (HER) and Zn dendrite formation. The obtained results confirm that the AV‐based electrolyte enhances the electrochemical stability and boosts the performance of the ZIBs. The formulated AV‐based electrolyte in symmetrical Zn//Zn cells demonstrates an outstanding cycle life of 4500 h, significantly longer than the aqueous electrolytes for ZIBs. The quinone moiety of the AV‐based electrolytes provides higher specific capacities for VO2(D) and activated carbon cathodes in full devices. AV‐based green electrolytes allow the realization of sustainable and safe energy storage systems for next‐generation applications. [ABSTRACT FROM AUTHOR]

Zinc metal stands out as a promising anode material due to its exceptional theoretical capacity, impressive energy density, and low redox potential. However, challenges such as zinc dendrite growth, anode corrosion, and side reactions in aqueous electrolytes significantly impede the practical application of zinc metal anodes. Herein, 3‐(1‐pyridinio)‐1‐propanesulfonate (PPS) is introduced as a zwitterionic additive to achieve long‐term and highly reversible Zn plating/stripping. Due to the orientation polarization with the force of electric field, PPS additive with π–π conjugated pyridinio cations and strong coordination ability of sulfonate anion tends to generate a dynamic adsorption layer and build a unique water–poor interface. PPS with steric hindrance effect and strong coordination ability can attract solvated Zn2+, thereby promoting the desolvation process. Moreover, by providing a large number of nucleation sites and inducing zinc ion flow, the preferred orientation of the (002) crystal plane can be achieved. Therefore, the interfacial electrochemical reduction kinetics is regulated and uniform zinc deposition is ensured. Owing to these advantages, the Zn//Zn symmetrical cell with PPS additive exhibits remarkable cycling stability exceeding 2340 h (1 mA cm−2 and 1 mA h cm−2). The Zn//V2O5 full cell also delivers stable cycling for up to 6000 cycles. [ABSTRACT FROM AUTHOR]

Aqueous Zn ion batteries (AZIBs) represent a promising candidate for the next‐generation energy storage and conversion systems due to their high safety and cost‐effectiveness. However, sluggish kinetics arising from interface desolvation processes pose challenges in achieving high‐power density and long cycle life for AZIBs. Here, it is discovered for the first time that heterostructures utilize built‐in electric field forces to promote the desolvation process at the electrode‐electrolyte interface. Density functional theory (DFT) calculations and structural characterization demonstrate that heterogeneous structures simultaneously accelerate the desolvation process and enhance ion diffusion, resulting in the outstanding rate performance (160.9 mA h g−1 at 5 A g−1) of TiS2‐TiO2 heterostructures, far exceeding that of a conventional TiS2 electrode with 14.2% capacity retention. Meanwhile, the insertion/extraction of the desolvated charge carriers reduced the volume change of TiS2‐TiO2 material during the charging/discharging processes, enabling the long‐lasting cycling stability (108.6 mA h g−1 after 2000 cycles at 0.5 A g−1). This study provides instructive electrode design strategies for the construction of fast‐charging electrochemical energy storage systems. [ABSTRACT FROM AUTHOR]

The plating/stripping efficiency of zinc (Zn) is directly related to the efficiency of zinc utilization and cycle stability of the battery, which is affected by factors such as the solvated water‐related hydrogen evolution reaction (HER), Zn corrosion, and dendrite formation. Therefore, creating a weak solvate shell for Zn2+ with reduced solvated water molecules can promote stable deposition and stripping of the zinc anode. In this work, a novel approach using the concentrated charge effect of anions is proposed to remove the solvated water and improve the efficiency of Zn plating/stripping. 3 mol kg−1 (3 m) ZnCl2, Zn(ClO4)2, and Zn(BF4)2 electrolytes are used as the representatives to investigate how anions regulate the solvent shell of zinc ion to achieve high Zn plating/stripping Coulombic efficiency (CE). Computational results show that Cl− has a more concentrated charge compared to ClO4− and BF4−, indicating a stronger interaction with Zn2+. This concentrated charge effect reduces the number of water molecules in Zn2+ solvation structures. Benefiting from weak solvent structure, the average coulomb efficiency, and cycling stability of the Zn─Cu asymmetric cell using ZnCl2 electrolyte is better. Additionally, the Zn‐NaV3O8 full cell of the ZnCl2 electrolyte exhibits good electrochemical performance. [ABSTRACT FROM AUTHOR]

Zinc anodes of zinc metal batteries suffer from unsatisfactory plating/striping reversibility due to interfacial parasitic reactions and poor Zn2+ mass transfer kinetics. Herein, methoxy polyethylene glycol‐phosphate (mPEG‐P) is introduced as an electrolyte additive to achieve long anti‐calendar aging and high‐rate capabilities. The polyanionic of mPEG‐P self‐assembles via noncovalent‐interactions on electrode surface to form polyether‐based cation channels and in situ organic–inorganic hybrid solid electrolyte interface layer, which ensure rapid Zn2+ mass transfer and suppresses interfacial parasitic reactions, realizing outstanding cycling/calendar aging stability. As a result, the Zn//Zn symmetric cells with mPEG‐P present long lifespans over 9000 and 2500 cycles at ultrahigh current densities of 120 and 200 mA cm−2, respectively. Besides, the coulombic efficiency (CE) of the Zn//Cu cell with mPEG‐P additive (88.21%) is much higher than that of the cell (36.4%) at the initial cycle after the 15‐day calendar aging treatment, presenting excellent anti‐static corrosion performance. Furthermore, after 20‐day aging, the Zn//MnO2 cell exhibits a superior capacity retention of 89% compared with that of the cell without mPEG‐P (28%) after 150 cycles. This study provides a promising avenue for boosting the development of high efficiency and durable metallic zinc based stationary energy storage system. [ABSTRACT FROM AUTHOR]

Highlights Negative charged acidic polarity (NCAP) has been unveiled as the guideline for selecting additives to regulate electric double layer (EDL) for Zn-ion batteries. NCAP glutamate has been verified to regulate EDL structure with synergetic effects, including preferential adsorption on Zn anode and reconstruction of hydrated Zn-ion clusters. Adding NCAP additives, Zn|Cu half-cell achieves a high Coulombic efficiency of 99.83% for 2000 cycles, and NH4V4O10|Zn full cell realizes a high-capacity retention of 82.1% for 3000 cycles.

Highlights: Negative charged acidic polarity (NCAP) has been unveiled as the guideline for selecting additives to regulate electric double layer (EDL) for Zn-ion batteries. NCAP glutamate has been verified to regulate EDL structure with synergetic effects, including preferential adsorption on Zn anode and reconstruction of hydrated Zn-ion clusters. Adding NCAP additives, Zn|Cu half-cell achieves a high Coulombic efficiency of 99.83% for 2000 cycles, and NH4V4O10|Zn full cell realizes a high-capacity retention of 82.1% for 3000 cycles. Zinc-ion batteries are promising for large-scale electrochemical energy storage systems, which still suffer from interfacial issues, e.g., hydrogen evolution side reaction (HER), self-corrosion, and uncontrollable dendritic Zn electrodeposition. Although the regulation of electric double layer (EDL) has been verified for interfacial issues, the principle to select the additive as the regulator is still misted. Here, several typical amino acids with different characteristics were examined to reveal the interfacial behaviors in regulated EDL on the Zn anode. Negative charged acidic polarity (NCAP) has been unveiled as the guideline for selecting additive to reconstruct EDL with an inner zincophilic H2O-poor layer and to replace H2O molecules of hydrated Zn2+ with NCAP glutamate. Taking the synergistic effects of EDL regulation, the uncontrollable interface is significantly stabilized from the suppressed HER and anti-self-corrosion with uniform electrodeposition. Consequently, by adding NCAP glutamate, a high average Coulombic efficiency of 99.83% of Zn metal is achieved in Zn|Cu asymmetrical cell for over 2000 cycles, and NH4V4O10|Zn full cell exhibits a high-capacity retention of 82.1% after 3000 cycles at 2 A g−1. Recapitulating, the NCAP principle posted here can quicken the design of trailblazing electrolyte additives for aqueous Zn-based electrochemical energy storage systems. [ABSTRACT FROM AUTHOR]

TiS2 has received significant attention as a promising anode for "Rocking‐Chair"‐type aqueous Zn‐ion batteries due to the large interlayer spacing and low discharge plateau. However, the structural distortion caused by the embedding of divalent Zn2+ as well as the undesirable hydrogen evolution reaction (HER) severely affects their cycling stability. Herein, a facet‐dependent mechanism is first deeply investigated to understand charge storage behaviors of TiS2 via differential electrochemical mass spectrometry, in situ electrochemical quartz crystal microbalance, and in situ X‐ray diffraction characterizations. By regulating the exposed crystal facets of TiS2 from (001) (TS (001)) to (011) (TS(011)), HER can be effectively inhibited, and the charge storage mechanism is transformed from Zn2+ insertion/extraction dominating to H+ insertion/extraction dominating, resulting in faster charge transfer kinetics and strong structure stability during long‐term cycling. Hence, TS(011) delivers a higher reversible capacity of 212.9 mAh g−1 at 0.1 A g−1 and a strong cycling stability of 74% capacity retention over 1000 cycles, much better than that of TS (001) with a reversible capacity of 164.7 mAh g−1 at 0.1 A g−1, a capacity retention of 17% after 1000 cycles. These new findings can provide deep insight into the rational design of high‐performance intercalation‐type electrode materials for energy storage applications. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (AZIBs) hold great potential for grid‐scale energy storage systems, owing to their intrinsic safety and low cost. Nevertheless, their industrialization faces challenges of severe Zn dendrites and parasitic reactions. In this study, sulfonated cellulose separator (denoted as CF‐SO3) with low thickness, exceptional mechanical strength, and large ionic conductivity is developed. Benefiting from the electrostatic repulsion between ─SO3− functional groups and SO42− anions and the strongly interaction between ─SO3− and Zn2+ cations, the migration of SO42− anions can be restricted, the 2D diffusion of Zn2+ ions at the surface of Zn electrode can be suppressed, and the desolvation of hydrated Zn2+ ions can be promoted. Concurrently, the homogeneous nanochannels within CF‐SO3 separator can ensure uniform electric field and Zn2+ ion flux. With these benefits, the CF‐SO3 separator enables Zn//Zn cells to run stably for 1200 h at 4 mAh cm−2 by facilitating oriented and dendrite‐free Zn deposition. Under a large depth of discharge of 68.3%, a life span of 400 h can still be achieved. Additionally, the reliability of CF‐SO3 separator is confirmed in Zn//MnO2 and Zn//H11Al2V6O23.2 full batteries with high mass loading conditions. This work provides valuable guidance for the advancement of high‐performance separators of AZIBs. [ABSTRACT FROM AUTHOR]

The reversibility and sustainability of Zn anode are greatly hampered by the dendrite growth and side reactions. Orientational deposition, which allows the assembly of Zn deposits in a highly ordered and compact manner, offers a solution to these issues by enabling dendrite‐free Zn anodes. Moreover, Zn orientational deposition can effectively inhibit side reaction by reducing the exposed surface area of the electrode. Despite significant progress in the field of Zn orientational deposition, there is still a lack of clear guidelines for regulating the orientation, and the underlying mechanisms remain rather elusive. Therefore, a comprehensive review is urgently needed to provide a mechanistic insight into Zn orientational deposition. This review summarizes the burgeoning strategies for steering Zn orientational deposition, categorizing the corresponding mechanisms into five aspects: heteroepitaxial deposition, homoepitaxial deposition, interfacial cultivation, crystal facet anchoring, and current density regulation. The distinct advantages and limitations of each mechanism in controlling the growth orientation are discussed in detail. Finally, the challenges and future trends pertaining to Zn orientational deposition are envisaged, aiming in essence to realize highly reversible Zn anodes and ultimately bridge the gap between reality and ideal in aqueous Zn‐ion batteries. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐ion batteries (ZIBs) are promising next‐generation energy storage devices, yet suffer from the issues of hydrogen evolution reaction (HER) and intricate side reactions on the Zn anode surface. The hydrogen (H)‐bond networks play a critical role in interfacial proton transport that may closely relate to HER but are rarely investigated. Herein, we report a self‐assembled monolayer (SAM) strategy which is constructed by anchoring ionic liquid cations on Ti3C2Tx substrate for HER‐free Zn anode. Molecule dynamics simulations reveal that the rationally designed SAM with a high coordination number of water molecules (25–27, 4–6 for Zn2+) largely reduces the interfacial densities of H2O molecules, therefore breaking the connectivity of H‐bond networks and blocking proton transport on the interface, by which the HER is suppressed. Then, a series of in situ characterizations demonstrate that negligible amounts of H2 gas are collected from the Zn@SAM‐MXene anode. Consequently, the symmetric cell enables a long‐cycling life of 3000 h at 1 mA cm−2 and 1000 h at 5 mA cm−2. More significantly, the stable Zn@SAM‐MXene films are successfully used for coin full cells showing high‐capacity retention of over 94 % after 1000 cycles and large‐area (10×5 cm2) pouch cells with desired performance. [ABSTRACT FROM AUTHOR]

Aqueous zinc ion batteries (AZIBs) have stimulated extensive attention due to their environmental friendliness and low cost. Unfortunately, the inevitable dendrite growth and corrosion on the zinc (Zn) anode severely hinder the practical application of AZIBs. Herein, an amino acid containing an imidazole group is introduced as an effective additive to address these issues. The dynamic conversion of amino acid and protonated amino acid creates a pH buffer function that regulates solution pH in real time, inhibits hydrogen evolution reaction (HER), and eliminates notorious by‐products. In addition, the protonated amino acid is preferentially adsorbed on the Zn anode, preventing contact of the active water with the Zn surface and promoting homogeneous Zn deposition. Thus, the amino acid‐based electrolyte promotes dendrite free plating/stripping with a Coulombic efficiency up to 99.67% and cycle lifetime of 2600 h. In particular, a depth of discharge of up to 87% can be achieved with an ultra‐high areal capacity of 24 mAh cm−2. The developed Zn||CVO full cell also exhibits better electrochemical performance than that without additives. This work provides an effective and convenient approach for safe and efficient Zn‐ion batteries. [ABSTRACT FROM AUTHOR]

The prepared NVOY electrode achieves high stability and excellent cycle performance for AZIBs by embedding polypyrrole in ammonium vanadate layers to remove excess ammonium ions, expand the interlayer spacing, and enhance electronic conductivity. [Display omitted] Ammonium vanadate with stable bi-layered structure and superior mass-specific capacity have emerged as competitive cathode materials for aqueous rechargeable zinc-ion batteries (AZIBs). Nevertheless, fragile N H...O bonds and too strong electrostatic interaction by virtue of excessive NH 4 + will lead to sluggish Zn2+ ion mobility, further largely affects the electro-chemical performance of ammonium vanadate in AZIBs. The present work incorporates polypyrrole (PPy) to partially replace NH 4 + in NH 4 V 4 O 10 (NVO), resulting in the significantly enlarged interlayers (from 10.1 to 11.9 Å), remarkable electronic conductivity, increased oxygen vacancies and reinforced layered structure. The partial removal of NH 4 + will alleviate the irreversible deammoniation to protect the laminate structures from collapse during ion insertion/extraction. The expanded interlayer spacing and the increased oxygen vacancies by the virtue of the introduction of polypyrrole improve the ionic diffusion, enabling exceptional rate performance of NH 4 V 4 O 10. As expected, the resulting polypyrrole intercalated ammonium vanadate (NVOY) presents a superior discharge capacity of 431.9 mAh g−1 at 0.5 A g−1 and remarkable cycling stability of 219.1 mAh g−1 at 20 A g−1 with 78 % capacity retention after 1500 cycles. The in-situ electrochemical impedance spectroscopy (EIS), in-situ X-ray diffraction (XRD), ex-situ X-ray photoelectron spectroscopy (XPS) and ex-situ high resolution transmission electron microscopy (HR-TEM) analysis investigate a highly reversible intercalation Zn-storage mechanism, and the enhanced the redox kinetics are related to the combined effect of interlayer regulation, high electronic conductivity and oxygen defect engineering by partial substitution NH 4 + of PPy incorporation. [ABSTRACT FROM AUTHOR]

The practical application of aqueous Zn‐ion batteries (AZIBs) is hindered by the crazy Zn dendrites growth and the H2O‐induced side reactions, which rapidly consume the Zn anode and H2O molecules, especially under the lean electrolyte and Zn anode. Herein, a natural disaccharide, d‐trehalose (DT), is exploited as a novel multifunctional co‐solvent to address the above issues. Molecular dynamics simulations and spectral characterizations demonstrate that DT with abundant polar −OH groups can form strong interactions with Zn2+ ions and H2O molecules, and thus massively reconstruct the coordination structure of Zn2+ ions and the hydrogen bonding network of the electrolyte. Especially, the strong H‐bonds between DT and H2O molecules can not only effectively suppress the H2O activity but also prevent the rearrangement of H2O molecules at low temperature. Consequently, the AZIBs using DT30 electrolyte can show high cycling stability even under lean electrolyte (E/C ratio = 2.95 µL mAh−1), low N/P ratio (3.4), and low temperature (−12 °C). As a proof‐of‐concept, a Zn||LiFePO4 pack with LiFePO4 loading as high as 506.49 mg can be achieved. Therefore, DT as an eco‐friendly multifunctional co‐solvent provides a sustainable and effective strategy for the practical application of AZIBs. [ABSTRACT FROM AUTHOR]

N‐type organic compounds present themselves as promising high‐capacity cathodes for aqueous Zn‐ion batteries. However, a common challenge is their working voltages often falling below 1 V versus Zn2+/Zn. To bridge this gap, a high‐voltage organic material is first developed, 5,6,11,12‐tetraazanaphthacene (TANC), using a heteroatomic substitution strategy. TANC feature a large π‐conjugated plane enriched with π−π interactions, which not only enhancing structural stability but also boosting charge transfer kinetics. The TANC cathode is achieved from its dihydro precursor, denoted as 2H‐TANC, via a facile in situ activation process within the battery itself. This electrochemical synthesis method is cost‐effective and environmentally friendly compared to traditional chemical method. The cathode shows a record‐high discharge voltage of 1.15 V (vs Zn2+/Zn) among n‐type organic materials and maintains cycling stability over 47,500 cycles. Furthermore, spent TANC electrodes can be efficiently recycled via a simple extraction process. The work marks a significant step toward the development of high‐voltage, affordable, and recyclable organic electrode materials, steering them to the forefront of future sustainable battery technologies. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous Zn‐ion batteries (AZIBs) are one of the most promising alternatives for traditional energy‐storage devices because of their low cost, abundant resources, environmental friendliness, and inherent safety. However, several detrimental issues with Zn metal anodes including Zn dendrite formation, hydrogen evolution, corrosion and passivation, should be considered when designing advanced AZIBs. Moreover, these thorny issues are not independent but mutually reinforcing, covering many technical and processing parameters. Therefore, it is necessary to comprehensively summarize the issues facing Zn anodes and the corresponding strategies to develop roadmaps for the development of high‐performance Zn anodes. Herein, the failure mechanisms of Zn anodes and their corresponding impacts are outlined. Recent progress on improving the stability of Zn anode is summarized, including structurally designed Zn anodes, Zn alloy anodes, surface modification, electrolyte optimization, and separator design. Finally, this review provides brilliant and insightful perspectives for stable Zn metal anodes and promotes the large‐scale application of AZIBs in power grid systems. [ABSTRACT FROM AUTHOR]

Abstract Rechargeable aqueous zinc (Zn) ion batteries (AZIBs) are gaining popularity in large‐scale energy storage due to their low cost, high safety, and environmental friendliness; however, dendrite growth and side reactions in Zn metal anodes limit their practical applications. Additionally, the difficulty of developing successful passivation of Zn anodes, combined with large‐area coating of protective layers, remains a major limitation to the commercialization of AZIBs. Here, we introduce two‐dimensional (2D) nanomaterials including MoS2, h‐BN, and Ti3C2Tx MXene as protective layers for Zn anodes, created on a Zn surface using a scalable, large‐area spray‐coating process. Examinations of electrochemical performance‐related material characterizations revealed that a specific type of 2D material with an optimal thickness prevents vertical growth of Zn dendrites, as well as side reactions including hydrogen evolution and corrosion, resulting in stable device operation with minimal overpotential and extended life, even under harsh measurement conditions. The highly stable MoS2@Zn anode allowed the MoS2@Zn//MnO2 full cell to achieve significantly more stable capacity retention, compared with the bare Zn//MnO2 cell. Our versatile and scalable solution‐based coating technique for easily forming large‐area 2D protective layers on Zn anodes offers new insights concerning improvements to AZIB reliability and performance.

Aqueous Zn‐ion batteries with mild acidic electrolytes are considered the promising energy storage solutions due to their outstanding merits of high energy density and cost‐effectiveness. However, the rampant dendrite growth and severe parasitic reactions caused by a series of factors such as irregular Zn2+ transport pathway and pH variation would result in poor cycling stability. Herein, a self‐regulated interface strategy implemented by ammonium persulfate ((NH4)2S2O8, denoted as APS) multifunctional additive is proposed to simultaneously address the above issues. The zincophilic NH4+ preferentially adsorbs on the Zn protuberance to exclude water molecules and shield the "tip effect," thus inhibiting side‐reactions and inducing uniform Zn deposition. Moreover, NH4+ and S2O82− can dynamically adjust H+ and OH− concentrations in a pH self‐buffer manner, thus effectively mitigating hydrogen evolution reaction and formation of by‐products. Consequently, with the existence of APS additive, Zn anode exhibits ultrahigh coulombic efficiency (CE) of 99.9% over 9000 cycles and ultra‐long lifespan of 4300 h at 5 mA cm−2. Furthermore, even under high NH4V4O10 mass loading (9.4 mg cm−2) and thin zinc foil (10 µm), the assembled NH4V4O10//Zn pouch cell with APS additive can still maintain stably over 210 cycles, demonstrating its excellent value for application. [ABSTRACT FROM AUTHOR]

The advanced aqueous zinc–ion batteries (AZIBs) are still challenging due to the harmful reactions including hydrogen evolution and corrosion. Here, a natural small molecule acid vitamin C (Vc) as an aqueous electrolyte additive has been selectively identified. The small molecule Vc can adjust the d band center of Zn substrate which fixes the active H+ so that the hydrogen evolution reaction (HER) is restrained. Simultaneously, it could also fine–tune the solvation structure of Zn ions due to the enhanced electrostatics and reduced Pauli repulsion verified by energy decomposition analysis (EDA). Hence, the cell retains an ultra–long cycle performance of over 1300 cycles and a superior Coulombic efficiency (CE) of 99.5 %. The prepared full cells display increased rate capability, cycle lifetime, and self–discharge suppression. Our results shed light on the mechanistic principle of electrolyte additives on the performance improvement of ZIBs, which is anticipated to render a new round of studies. [ABSTRACT FROM AUTHOR]

The utilization rate of active sites in cathode materials for Zn‐based batteries is a key factor determining the reversible capacities. However, a long‐neglected issue of the strong electrostatic repulsions among divalent Zn2+ in hosts inevitably causes the squander of some active sites (i.e. gap sites). Herein, we address this conundrum by unraveling the "gap‐filling" mechanism of multiple charge carriers in aqueous Zn‐MoS2 batteries. The tailored MoS2/(reduced graphene quantum dots) hybrid features an ultra‐large interlayer spacing (2.34 nm), superior electrical conductivity/hydrophilicity, and robust layered structure, demonstrating highly reversible NH4+/Zn2+/H+ co‐insertion/extraction chemistry in the 1 M ZnSO4+0.5 M (NH4)2SO4 aqueous electrolyte. The NH4+ and H+ ions can act as gap fillers to fully utilize the active sites and screen electrostatic interactions to accelerate the Zn2+ diffusion. Thus, unprecedentedly high rate capability (439.5 and 104.3 mAh g−1 at 0.1 and 30 A g−1, respectively) and ultra‐long cycling life (8000 cycles) are achieved. [ABSTRACT FROM AUTHOR]

Benefiting from the advantageous features of low manufacturing cost, inherent safety and resource renewability, aqueous Zn-ion batteries (AZIBs) are considered as one of the most promising candidates for energy storage systems. Unfortunately, problems of AZIBs such as cathode dissolution, Zn dendrite growth, and irreversible electrochemical side reactions have restricted the implementation for practical applications. Vanadium-based are deemed as hopeful cathode materials for AZIBs owing to diverse crystal structures and multiple valence states. Therefore, it is necessary to comprehensively summarize the advance facing vanadium-based cathodes and the corresponding progress to create roadmaps for the development of high-stability AZIBs. This review starts with a discussion of the storage and failure mechanisms of AZIBs and their related affects. Then, enormous up-to-date achievements of vanadium-based cathode materials are highlighted, including vanadium-based oxides and metal vanadium-based oxides. The challenges associated with the application of vanadium-based compounds in AZIBs are also highlighted, and effective strategies to overcome them are proposed. Finally, perspectives and directions on further optimizing vanadium-based cathode materials to improve the performance of AZIBs are discussed.

Aqueous zinc‐ion batteries (AZIBs) are emerging as one of the most reliable energy storage technologies for scale‐up applications, but still suffer from the instability of Zn anode, which is mainly caused by the undesirable dendrite growth and side reactions. To tackle these issues, we formulate a new aqueous electrolyte with weak solvation effect by introducing low‐dielectric‐constant acetone to achieve H2O‐poor solvation structure of Zn2+. Experimental and theoretical calculation studies concurrently reveal that such solvation structure can: i) relieve the solvated H2O related side reactions, ii) suppress the dendrite growth by boosting the desolvation kinetics of Zn2+ and iii) in situ form solid electrolyte interface (SEI) to synergistically inhibit the side reaction and dendrite growth. The synergy of these three factors prolongs the cycling life of Cu/Zn asymmetric cell from 30 h to more than 800 h at 1 mA cm−2/1 mAh cm−2, and can work at more harsh condition of 5 mA cm−2/5 mAh cm−2. More encouragingly, Zn/V2O5 ⋅ nH2O full cell also shows enhanced cycling stability of 95.9 % capacity retention after 1000 cycles, much better than that with baseline electrolyte (failing at ≈700th cycle). [ABSTRACT FROM AUTHOR]

Highlights: γ-MnO2 loaded on N-doped biomass carbon from grapefruit peel is firstly developed. The splendid cathodic properties (e.g., coulombic efficiency: ~ 100%, energy density: 553.12 Wh kg−1) are gained. The biomass strategy guaranteed via cytotoxicity test shows a clinical potential. Zn-ion storage efficiency is boosted mainly by regulating Mn–O bond and Mn domains. Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future. Therefore, γ-MnO2 uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work, and particularly the composite cathode with carbon carrier quality percentage of 20 wt% delivers the specific capacity of 391.2 mAh g−1 at 0.1 A g−1, outstanding cyclic stability of 92.17% after 3000 cycles at 5 A g−1, and remarkable energy density of 553.12 Wh kg−1 together with superior coulombic efficiency of ~ 100%. Additionally, the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments, which verifies its tremendous potential in the application of clinical medicine. Besides, Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of Jahn–Teller effect and Mn domains distribution combined with theoretical analysis and experimental data. Thus, a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (ZIBs) have been regarded as a promising candidate for the next‐generation energy‐storage devices due to their intrinsic safety, low cost, resource abundance, and environmental friendliness. Nevertheless, the commercial applications of ZIBs have been largely plagued by the instability of the Zn anodes. Interfacial engineering arises as a straightforward and effective method to address the instability issues for the development of high‐performance ZIBs. In this review, a comprehensive overview of recent progress and perspective in interfacial engineering techniques to stabilize Zn anodes in ZIBs is presented. With emphasis on the critical issues regarding the instability problems, including Zn dendrites, hydrogen evolution reaction (HER), corrosion and passivation, the major effects and the underlying mechanisms are analyzed, and the corresponding interfacial engineering strategies as well as analytical technologies are summarized. The existing challenges and opportunities in interfacial engineering are also prospected for the future development of high‐performance ZIBs. [ABSTRACT FROM AUTHOR]

Zn‐ion batteries are regarded as the most promising batteries for next‐generation, large‐scale energy storage because of their low cost, high safety, and eco‐friendly nature. The use of aqueous electrolytes results in poor reversibility and leads to many challenges related to the Zn anode. Electrolyte additives can effectively address many such challenges, including dendrite growth and corrosion. This review provides a comprehensive introduction to the major challenges in and current strategies used for Zn anode protection. In particular, an in‐depth and fundamental understanding is provided of the various functions of electrolyte additives, including electrostatic shielding, adsorption, in situ solid electrolyte interphase formation, enhancing water stability, and surface texture regulation. Potential future research directions for electrolyte additives used in aqueous Zn‐ion batteries are also discussed. [ABSTRACT FROM AUTHOR]

Over the past decades, there has been a growing interest in rechargeable aqueous Zn‐ion batteries (AZIBs) as a viable substitute for lithium‐ion batteries. This is primarily due to their low cost, lower redox potential, and high safety. Nevertheless, the progress of Zn metal anodes has been impeded by various challenges, including the growth of dendrites, corrosion, and hydrogen evolution reaction during repeated cycles that result in low Coulombic efficiency and a short lifetime. Therefore, we represent recent advances in Zn metal anode protection for constructing high‐performance AZIBs. Besides, we show in‐depth analyses and supposed hypotheses on the working mechanism of these issues associated with mildly acidic aqueous electrolytes. Meanwhile, design principles and feasible strategies are proposed to suppress dendrites' formation of Zn batteries, including electrode design, electrolyte modification, and interface regulation, which are suitable for restraining corrosion and hydrogen evolution reaction. Finally, the current challenges and future trends are raised to pave the way for the commercialization of AZIBs. These design principles and potential strategies are applicable in other metal‐ion batteries, such as Li and K metal batteries. [ABSTRACT FROM AUTHOR]

The cyclability of aqueous zinc‐ion batteries is greatly influenced by Zn dendrites and parasitic reactions. Although separator modifications have proven to be effective in addressing these issues, most of the developed separators are too thick to meet practical requirements. Herein, an amino (−NH2)‐functionalized Zr‐based metal–organic framework (MOF), i.e., UiO‐66‐NH2, is incorporated into lignocellulose separator. The amino functional groups not only possess good zincophilicity but also strongly interact with H2O molecules through hydrogen bonding. Therefore, the abundant intersecting subnano‐sized channels within UiO‐66‐NH2 act as desolvation sieves and facilitate the migration and uniform distribution of Zn2+ ions. Even at a rather low thickness of 20 µm, the modified separator can significantly improve the reversibility of Zn electrochemistry and suppress water‐induced hydrogen evolution. With the use of this separator, the Zn electrodes demonstrate a working life exceeding 2000 h at a current density of 2 mA cm−2 with remarkable dendrite‐free characteristic and remain operationally viable under ultrahigh areal capacity of 25 mAh cm−2. Additionally, the resultant Zn//MnO2 battery provides superior rate capability and excellent cyclability. This study provides novel insights into the utilization of amino functional groups to inhibit unfavorable phenomena in aqueous batteries. [ABSTRACT FROM AUTHOR]