Rechargeable Zn-ion Batteries Research Articles

Thickness-Controlled Synthesis of Compact and Uniform MOF Protective Layer for Zinc Anode to Achieve 85% Zinc Utilization.

Zinc anode-based aqueous batteries have attracted considerable interest for large-scale energy storage and wearable devices. Unfortunately, the formation of Zn dendrite, parasitic hydrogen evolution reaction (HER), and irreversible by-products, seriously restrict their practical applications. Herein, a series of compact and uniform metal-organic frameworks (MOFs) films with precisely controlled thickness (150-600nm) are constructed by a pre-oxide gas deposition (POGD) method on Zn foil. Under the protection of MOF layer with optimum thickness, the corrosion of zinc, the side reaction of hydrogen evolution, and the growth of dendrites on the zinc surface are suppressed. The symmetric cell based on Zn@ZIF-8 anode exhibits exceptional cyclicality for over 1100h with low voltage hysteresis of≈38mV at 1mAcm-2 . Even at current densities of 50mAcm-2 with an area capacity of 50mAhcm-2 (85%Zn utilization), the electrode can keep cycling for >100h. Besides, this Zn@ZIF-8 anode also delivers a high average CE of 99.4% at 1mAcm-2 . Moreover, a rechargeable Zn ion battery is fabricated based on the Zn@ZIF-8 anode and MnO2 cathode, which presents an exceptionally long lifespan with no capacity attenuation for 1000 cycles.

Enhancing electrochemical performance in aqueous rechargeable Zn-ion batteries through bimetallic oxides of manganese and cobalt as electrode

The capacity of Co3O4//Zn batteries is decreased by the volume change of Co3O4 cathode in practical application, so its advantages are not fully utilized. To improve the capacity of Co3O4//Zn battery, a cathode of Mn-doped Co3O4 based on carbon cloth in aqueous zinc-ion battery was successfully prepared by one-step hydrothermal. Compared to existing preparation processes, greatly reducing preparation time and cost, and the Mn-doped Co3O4 cathode had a unique mesoporous microsphere structure. The battery in aqueous electrolyte had a high charge/discharge voltage of 2.2 V, a high specific capacity of 279.3 mAh/g at 1 A/g, outstanding rate capability, a high energy density of 863.15 Wh/kg, a high power of 1327.9W/Kg and superior cycle stability of 97% capacity retention over 1000 cycles at 5 A/g. The improvement in electrode material provided a new idea for preparing new mesoporous Co3O4 nanocomposites.

Establishing aqueous zinc-ion batteries for sustainable energy storage

Aqueous rechargeable Zn-ion batteries (ARZIBs) have been becoming a promising candidates for advanced energy storage owing to their high safety and low cost of the electrodes. However, the poor cyclic stability and rate performance of electrodes severely hinder their practical applications. Here, an ARZIBs configuration consisting of Cr3+-substituted Cu-Rich Prussian blue analogues (CuCrFe(CN)6) cathode, electrodeposited zinc nanosheets on copperclad carbon framework (ZnNS@CuCF) anode, and Zn(OTf)2-based electrolyte with ethylene sulfate (DTD) that are proposed. Combining the in situ characterization, ex situ synchrotron radiation and density functional theory (DFT) calculations, the Cr3+-substitution and K+ extraction can effectively lower the band gap of the electrodes and Zn ion diffusion activation energy. Thus, the assembled ARZIBs system delivers the excellent electrochemical performance such as large specific capacity of 183.9 mAh g−1, high energy density of 239.2 Wh kg−1 and impressive cyclic stability with the capacity retention of 92.4% after 13,000 discharging/charging cycles.

Monitoring the Cation Coordination Sphere Using Hydrated Eutectic Electrolyte for Better Cyclic Stability and High Energy Density Zn-Ion Battery

Aqueous rechargeable Zn-ion batteries (ZiBs) are receiving increasing attention worldwide owing to their inherent safety and cost effectiveness. However, ZiBs are still struggling with rapid performance degradation caused by poor Zn anode reversibility and cathode dissolution into aqueous electrolytes. Inspired by the knowledge of industrial-scale Zn electroplating, a cyanide functional group containing a succinonitrile (SN) neutral ligand-based hydrated eutectic electrolyte was used to mitigate these issues. The ligand-oriented SN partially replaced free water molecules from the Zn2+ ion primary solvation sheath, resulting in delayed oxidation and a smaller Zn2+ ion desolvation energy barrier which promoted uniform Zn nucleation. Moreover, the MoO3@Mn3O4 cathode and Zn anode-based ZiB in an eutectic hydrated electrolyte with a 10:10 molar ratio of ZnCl2 and SN exhibited an ∼2.3 V working potential window which delivered a maximum of ∼476 mAh g–1 specific capacity and ∼232.2 Wh kg–1 energy density at a 0.2 A g–1 current density. The fabricated device exhibited ∼79.56% specific capacity retention after 5000 cycles at a 10 A g–1 current density. The coinsertion/extraction of H+ and Zn2+ ions and the Zn deposition/dissolution mechanism of the optimized hydrated eutectic electrolyte-based ZiBs are investigated by ex situ physicochemical and electrochemical studies. Overall, this work provides a new path on exploring green electrolytes and layered-structure materials for the development of high-performance ZiBs.

Materials and structural design for preferable Zn deposition behavior toward stable Zn anodes

AbstractBenefiting from the high capacity of Zn metal anodes and intrinsic safety of aqueous electrolytes, rechargeable Zn ion batteries (ZIBs) show promising application in the post‐lithium‐ion period, exhibiting good safety, low cost, and high energy density. However, its commercialization still faces problems with low Coulombic efficiency and unsatisfied cycling performance due to the poor Zn/Zn2+ reversibility that occurred on the Zn anode. To improve the stability of the Zn anode, optimizing the Zn deposition behavior is an efficient way, which can enhance the subsequent striping efficiency and limit the dendrite growth. The Zn deposition is a controlled kinetics‐diffusion joint process that is affected by various factors, such as the interaction between Zn2+ ions and Zn anodes, ion concentration gradient, and current distribution. In this review, from an electrochemical perspective, we first overview the factors affecting the Zn deposition behavior and summarize the modification principles. Subsequently, strategies proposed for interfacial modification and 3D structural design as well as the corresponding mechanisms are summarized. Finally, the existing challenges, perspectives on further development direction, and outlook for practical applications of ZIBs are proposed.

An Overview of Challenges and Strategies for Stabilizing Zinc Anodes in Aqueous Rechargeable Zn-Ion Batteries

Aqueous rechargeable zinc ion batteries (ZIBs) have been revived and are considered a promising candidate for scalable electrochemical energy storage systems due to their intrinsic safety, low cost, large abundance, mature recyclability, competitive electrochemical performance, and sustainability. However, the deployment of aqueous rechargeable ZIBs is still hampered by the poor electrochemical stability and reversibility of Zn anodes, which is a common, inherent issue for most metal-based anodes. This review presents a comprehensive and timely overview of the challenges and strategies of Zn anodes toward durable ZIBs. First, several challenges that significantly reduce the Coulombic efficiency and cycling stability of Zn anodes are briefly discussed including dendrite formation, hydrogen evolution, and corrosion. Then, the mitigation strategies are summarized in terms of modifying the electrode/electrolyte interfaces, designing electrode structures, and optimizing electrolytes and separators. Further, we comprehensively discuss the mechanisms behind these issues and improvement strategies with respect to the anodes, electrolytes, and separators. Lastly, we provide perspectives and critical analyses of remaining challenges, outlook, and future direction for accelerating the practical application of aqueous rechargeable ZIBs.

Boosting the capacity and stability of a MoO3 cathode via valence regulation and polypyrrole coating for a rechargeable Zn ion battery.

Molybdenum trioxide (MoO3) is emerging as a hugely competitive cathode material for aqueous zinc ion batteries (ZIBs) for its high theoretical capacity and electrochemical activity. Nevertheless, owing to its undesirable electronic transport capability and poor structural stability, the practical capacity and cycling performance of MoO3 are yet unsatisfactory, which greatly blocks its commercial use. In this work, we report an effective approach to first synthesise nanosized MoO3-x materials to provide more active specific surface areas, while improving the capacity and cycle life of MoO3 by introducing low valence Mo and coated polypyrrole (PPy). MoO3 nanoparticles with low-valence-state Mo and PPy coating (denoted as MoO3-x@PPy) are synthesized via a solvothermal method and subsequent electrodeposition process. The as-prepared MoO3-x@PPy cathode delivers a high reversible capacity of 212.4 mA h g-1 at 1 A g-1 with good cycling life (more than 75% capacity retention after 500 cycles). In contrast, the original commercial MoO3 sample only obtains a capacity of 99.3 mA h g-1 at 1 A g-1, and a cycling stability of 10% capacity retention over 500 cycles. Additionally, the fabricated Zn//MoO3-x@PPy battery obtains a maximum energy density of 233.6 W h kg-1 and a power density of 11.2 kW kg-1. Our results provide an efficient and practical approach to enhance commercial MoO3 materials as high-performance cathodes for AZIBs.

Mo-Pre-Intercalated MnO2 Cathode with Highly Stable Layered Structure and Expanded Interlayer Spacing for Aqueous Zn-Ion Batteries

Although manganese-based oxides possess high voltage and low cost, the sluggish reaction kinetics and poor structural stability hinder their applications in aqueous rechargeable Zn-ion batteries (ZIBs). Herein, a molybdenum (Mo) pre-intercalation strategy is proposed to solve the above issues of δ-MnO2. The pre-intercalated Mo dopants, acting as the interlayer pillars, can not only expand the interlayer spacing but also reinforce the layered structure of δ-MnO2, finally achieving enhanced reaction kinetics and superb cycling stability during carrier (de)intercalation. Moreover, oxygen defects, introduced due to Mo-pre-intercalation, play a critical role in the fast reaction kinetics and capacity improvement of the Mo-pre-intercalated δ-MnO2 (Mo-MnO2) cathode. Therefore, the Mo-MnO2 cathode displays a high energy density of 451 Wh kg-1 (based on cathode mass), excellent rate capability, and admirable long-term cycling performance with a high capacity of 159 mAhg-1 at 1.0 A g-1 after 1000 cycles. In addition, the energy storage mechanism of Zn2+/H+ stepwise reversible (de)intercalation is also revealed by ex situ experiments. This work provides an insightful guide for boosting the electrochemical performance of Mn-based oxide cathodes for ZIBs.

Enhanced cycling stability achieved by the nitrogen doped carbon coating layer for electrodeposited Mn3O4 in aqueous zinc ion batteries

Aqueous rechargeable Zn-ion batteries (ZIBs) are promising candidates for large scale energy storage. Unfortunately, their application is hindered by the quick capacity fading. Herein, the Mn3O4@N-doped carbon coated carbon cloth electrodes (Mn3O4@NC/CC) are prepared by electrodeposition and calcination and are used as the cathode for ZIBs. The thickness of the electrodeposited Mn3O4 is ∼ 200 nm, and the NC layer is ∼ 10 nm. The ZIB with Mn3O4@NC/CC displays the capacity of 265.8 mAh g−1 at 0.2 A g−1, and has a high reversible capacity of 165.6 mAh g−1 after 2000 charged − discharged cycles at 3 A g−1. The capacitive-controlled processes contribute mainly to the charge storage mechanism. The introduction of NC layer can effectively prevent the disintegration of active material during charge-discharge cycling. The NC layer can also hinder the diffusion of Zn2+ and enhance Rct, that leads to suppressed Zn ion insertion/extraction and possibly milder change in crystal structure. Ex-situ characterization shows that the Mn3O4 is irreversibly converted to R-MnO2 after multiple charge − discharge cycles, and both H+ and Zn2+ participate in the charge storage processes.

Manganese Molybdate Cathodes with Dual-Redox Centers for Aqueous Zinc-Ion Batteries: Impact of Electrolyte on Electrochemistry

Although bimetallic oxides have been shown to be beneficial as electrode materials in battery systems over their monometallic oxide counterparts, the implementation of metal molybdates with dual-redox centers has not been widely studied in aqueous rechargeable Zn-ion batteries. Manganese molybdate (MnMoO4) was synthesized via facile cosolvent coprecipitation and implemented as a cathode material for the first time in this system using 3 M ZnSO4 and 3 M ZnCl2 electrolytes to investigate the impact of the anion. In the two electrolytes, both manganese and molybdate metal centers were determined to be redox active using Mn and Mo K-edge operando X-ray absorption spectroscopies (XAS), with the corresponding voltage plateaus at 1.4 and 0.5 V, respectively. The difference in anions resulted in a preference regarding the active redox center, with the sulfate based preferring Mo redox and chloride based preferring Mn redox. Additionally, the redox reactions also differ in rate dependency, with Mn and Mo redox reactions preferring slow and fast current rates, respectively. In both systems, Mn redox was seen to be the more stable mechanism over prolonged cycling. The preference was related to the dissolution of the MnMoO4 material by applying Pearson’s hard–soft acid–base theory and considering the solubilities of the respective salts.

An in-situ electrochemical oxidation strategy of VPO4 and its performance as a cathode in aqueous Zn-ion batteries

• VPO 4 is reported as a new cathode for aqueous Zn-ion battery for the first time. • Due to in situ electrochemical oxidation process, the assembled cell exhibits the excellent electrochemical performance. • The detailed electrochemical oxidation process and Zn 2+ storage mechanism is discussed by In-situ XRD, ex-situ TEM and XPS. • A clear electrochemical kinetics of the assembled cell was also analyzed. Benefiting from the security and low cost, aqueous rechargeable Zn-ion batteries (ZIBs) have currently become attractive candidate devices for energy storage. However, the scarcity of appropriate materials served as cathodes is one of the major issues that hinder the development of aqueous ZIBs. VPO 4 is considered as a promising cathode material for energy storage with huge potential windows and high specific capacity due to the stable structure caused by the stable PO 4 polyanionic group and the various oxidation states of V element. However, due to the low valence state of V, as Zn 2+ host structure, PO 4 could not be effectively discharged directly. Herein, by an in situ electrochemical anodic oxidation method, we successfully improved the valence state of V and a higher valence vanadium-based compound (Zn 0.11 VO(PO 4 )•2.5H 2 O) was obtained. As expected, due to the increased valence state of V element and obviously reduced particle size caused the in situ electrochemical oxidation, the assembled Zn/VPO 4 cells exhibits high reversible specific capacity of about 210 mA h g −1 at 50 mA g −1 and a good rates cycling stability. Furthermore, the efficient in situ electrochemical oxidation process of VPO 4 cathode and the reversible Zn 2+ ions insertion/extraction mechanism in the subsequent cycles have been investigated through in situ XRD diffraction, field emission scanning electron microscopy (FESEM) and ex situ XRD photoelectron spectroscopy (XPS). This work also provides a novel method to design the high performance Zn ion cathode material.

15-Crown-5 ether as efficient electrolyte additive for performance enhancement of aqueous Zn-ion batteries

Aqueous rechargeable Zn-ion batteries (ZIBs) have been regarded as a complement to LIBs due to their merits in terms of high safety, low cost, environmentally benignity, and long cycle life. However, the Zn metal anode suffers from corrosion and parasitic reactions in the aqueous electrolyte, which lead to growth of byproduct flakes and hydrogen gas evolution in the Zn platting/stripping process. Here, an organic additive, 15-crown-5 ether (15-CE-5), is added into the aqueous ZnSO4 electrolyte to improve the Zn anode performance by altering the Zn2+ solvation sheath. Other CE molecules such as 12-CE-4 and 18-CE-6 are also tested, while their efficacies are inferior compared to that of 15-CE-5. The optimal concentration of 15-CE-5 in the ZnSO4 electrolyte is found to be 2 wt%, which enables the best performance of Zn anode in either Zn||Zn symmetric cells or MnO2||Zn full cells. Using this modified electrolyte, the Zn||Zn symmetric cell exhibits a cycle life of 770 h when tested at 2 mA cm−2 and a set capacity of 2 mAh cm−2, and the MnO2||Zn full cell shows enhanced and stable capacity over 1000 cycles. The experimental results are elucidated by theoretical studies including molecule dynamics simulations and density functional theory calculations.

Na superionic conductor-type compounds as protective layers for dendrites-free aqueous Zn-ion batteries

Aqueous rechargeable Zn-ion batteries (ARZIBs) have attracted much attention owing to their safety, high energy density and environmental friendliness. However, dendrite formation and corrosive reactions on Zn anode surface limit the development of ARZIBs. Here, Ga3+-doped NaV2(PO4)3 with Na superionic conductor (NASICON) structure [NVP-Ga(x), x = 0, 0.25, 0.5, 0.75] have been exploited as the high-efficiency artificial layer to stabilize Zn anode. The optimal NVP-Ga(0.5) layer can homogenize ion flux and promote uniform deposition of zinc, the dendrite growth and the parasitic reactions can be greatly inhibited. The symmetric cell based on this unique protection layer can stably operate over 1,300 h at 0.5 mA cm−2 with 0.5 mAh cm−2. Benefitting from the high-performance Zn metal anode, the full batteries paired with MnO2 cathode deliver a high discharge capacity of 106 mAh/g with the capacity retention rate of 85 % after 8,000 cycles. This work provides an advanced strategy to stabilize Zn anode for the industrialization of ARZIBs in the near future.

Potassium-doped hydrated manganese dioxide nanowires-carbon nanotubes on graphene for high-performance rechargeable zinc-ion batteries

Aqueous rechargeable Zn-ion batteries (ARZIB) are promising candidates for next-generation batteries because of their high safety, low cost, and relatively high capacity. In this study, we developed hydrated and potassium-doped manganese dioxide (MO) nanowires mixed with carbon nanotubes (CNT) on a graphene substrate (hydrated KMO-CNT/graphene) for ARZIB. A simple polyol process using poly(ethyl glycol), KMnO4, CNT, and graphene was utilized to fabricate hydrated KMO-CNT/graphene. MnO2 nanowires with diameters of 15–25 nm possess a high specific capacity with a short diffusion path. The intercalated K ions and hydrates in the layered MnO2 nanowires maintained the MO structure during the charge and discharge processes, whereas carbon nanomaterials (CNT and graphene) enhanced the conductivity of the material. Consequently, hydrated KMO-CNT/graphene demonstrated good ARZIB performance. A high capacity of 359.8 mAh g–1 at 0.1 A g–1, and at a high current density of 3.0 A g–1, a capacity of 129 mAh g–1 with 77% retention after 1000 cycles, were achieved.

A strategy to control crystal water content in hydrated vanadium oxide cathode for promoting aqueous rechargeable zinc-ion batteries

A simple hydrothermal route is used to prepare 3D porous hydrated vanadium oxide porous microspheres with different crystal water content. It is the first report that too much water molecule can lead to poor Zn storage performance and optimal structural water content is needed to improve electrochemical performance. By tuning the ratio of Zn to V during the synthesized process, Zn0.146V2O5∙0.579 H2O porous microspheres with optimal structural water content exhibit superior electrochemical performance for a promising aqueous rechargeable Zn-ion batteries. At the current density of 0.1 A g−1, it can register a high reversible discharge capacity of 416 mAh g−1. An initial discharge capacity can reach 192 mAh g−1 at the current density of 10.0 A g−1, the specific capacity remains at 202 mAh g−1 and the capacity retention is 105% after 10,000 cycles. Optimal structural water content as well as synergistic effect of pre-intercalated Zn2+ ions should be responsible for excellent electrochemical performance of cathode materials.

Crystal form modulation enables high-performance manganese dioxide cathode for aqueous zinc ion battery

Manganese dioxide (MnO2) is a promising cathode candidate for advanced rechargeable Zn-ion batteries (ZIBs) owing to its low cost, high theoretical capacity and high output voltage. However, the poor stability and low practical capacity has greatly hampered its commercialization. Herein, we demonstrate a crystal form modulation strategy to enhance the capacity and cycling durability of commercial γ-MnO2 as robust ZIBs cathode material. By introducing new β-MnO2 crystal form with compact (1 × 1) tunnel structure after simple calcination, the γ- and β- co-existed MnO2 (denoted as m-MO) shows enhanced electrical conductivity and structural stability. Consequently, the m-MO cathode exhibits an excellent capacity of 273.6 mAh g–1 at 0.25 A g–1 with good cycle stability, much higher than the pristine γ-MnO2 cathode (156.7 mAh g–1). Furthermore, an aqueous ZIBs based on m-MO cathode delivers a large peak energy density of 349.1 W h kg–1 at 0.322 kW kg–1 and power density of 4.77 kW kg–1 at 123.01 W h kg–1. This work presents an effective crystal form modulation strategy to construct high-performance ZIBs cathodes based on commercial MnO2, which is highly potential for further commercial applications.

A study on the synthesis of MoS2/rGO and the investigation of their charge-discharge properties when used as cathode material in a rechargeable Zn-ion battery

Recently, rechargeable aqueous Zn-ion batteries have attracted much attention and are potential candidates for grid storage applications because of their low cost and safety. However, to approach practical applications, suitable cathode materials must be developed. As a two-dimensional layered material, MoS2-based materials are very potential candidates. Herein, MoS2/rGO materials were synthesized by hydrothermal method and then the charge-discharge properties of the fabricated materials were investigated when they are used as cathode materials for rechargeable Zn-ion batteries. The MoS2/rGO has an expanded interlayer, which achieves a high initial capacity of about 170 mAh/g but does not have a high stability. In contrast, the MoS2-KOA has a low capacity but is very stable, even after 200 charge/discharge cycles. This study has shown the advantages and disadvantages of MoS2-based materials with expanded interlayer and suggests further work to find methods to stabilize the expanded interlayer to increase the charge/discharge stability.

Achieving high-rate and durable aqueous rechargeable Zn-Ion batteries by enhancing the successive electrochemical conversion reactions

The mild electrolyte working environment of rechargeable aqueous Zn-ion batteries (AZIBs) features its promising characteristic and potential application for large-scale energy storage system. However, the poor cycling stability significantly hinders the broad application of AZIBs due to the complex electrochemical conversion reactions during charge-discharge process. Herein, we propose a strategy to improve the electrochemical performance of AZIB by enhancing the successive electrochemical conversion reactions. With a rational design of electrode, an even homogeneous electric field can be achieved in the cathode side, resulting to significantly enhanced efficiency of successive electrochemical conversion reactions. Charge storage mechanism studies reveal that the reversibility behaviors of byproducts alkaline zinc sulfate (ZHS) can dramatically determine the H+/Zn2+ de/intercalation process, and a high reversibility characteristic ensures the facilitated electrochemical kinetics. As expected, the resultant AZIB possesses outstanding electrochemical performance with a high specific capacity of 425.08 mAh⋅g−1 at 0.1 A⋅g−1, an excellent rate capacity of about 60% (246.6 mAh⋅g−1 at 1 A⋅g−1) and superior cycling stability of 93.7% after 3000 cycles (at 3 A⋅g−1). This effective strategy and thinking proposed here may open a new avenue for the development of high-performing AZIBs.

Zincophilic 3D ZnOHF nanowire arrays with ordered and continuous Zn2+ Ion modulation layer enable long-term stable Zn metal anodes

Metallic Zn anode is a key component for aqueous rechargeable Zn-ion batteries (ZIBs) owing to its high theoretical capacity, low cost, and excellent safety. However, the practical applications remain impeded by dendritic growth and side reactions occurring at the Zn anode surface. Herein, a 3D ZnOHF nanowire array interface is for the first time in-situ built on Zn foil (ZnOHF NWs@Zn) through a hydrothermal method, and then used as an ordered and continuous Zn2+ ion modulation layer to guide the reversible and long-cycling Zn plating/stripping processes. As demonstrated by our density functional theory (DFT) calculations, the ZnOHF shows the desired superior zincophilic properties compared to pure Zn, enabling a low Zn nucleation energy and a fast Zn2+ ion diffusion. Moreover, the 3D ZnOHF NW architecture homogenizes the electric field distribution, thus modifying the subsequent Zn deposition process. Consequently, the thus-obtained ZnOHF NWs@Zn anode demonstrates a low Zn nucleation overpotential (87.8 at 5 mA cm−2), high Zn storage capacity (72.8 mAh cm−2) and excellent coulombic efficiency (exceeding 98.8%). The effectiveness of the ZnOHF NWs@Zn anode is also demonstrated through ZnOHF NWs@Zn//ZnOHF NWs@Zn symmetrical cell and MnO2@CC//ZnOHF NWs@Zn ZIB full cell, both with outstanding cycle stability.

Highly Strengthened and Toughened Zn–Li–Mn Alloys as Long‐Cycling Life and Dendrite‐Free Zn Anode for Aqueous Zinc‐Ion Batteries

Zn-ion batteries (ZIBs) using aqueous electrolyte, recently, have been a hot topic owing to the high safety, low cost, and high specific energy capacity. However, the formation of dendrite and side reactions on the Zn anode during cycling inhibit the application of ZIBs. An advanced Zn anode by alloying a small amount of Li and Mn with Zn is hereby reported. It is found that Li and Mn can form cationic ions which restrain lateral diffusion of Zn ions and regulate zinc electrodeposition through the electrostatic shield mechanism. As a result, the formation of Zn dendrite is greatly inhibited. This process also mitigates the formation of Zn-based byproduct and Zn passivation. Consequently, the symmetric ZnLiMn/ZnLiMn cell presents a small overpotential of 30mV at 1mA cm-2 , greatly enhanced cycling durability (1000 h at a current density of 1mA cm-2 ), and a dendrite-free morphology after cycles. Moreover, the authors find that the ZnLiMn alloy has greatly enhanced mechanical properties. The assembled ZnLiMn/MnO2 full cell can retain 96% capacity after 400 cycles at 1 C. Thus, the alloying low-cost Li/Mn strategy is very promising for large-scale production of dendrite-free Zn electrode in rechargeable ZIBs.