Zinc-based Batteries Research Articles

(Invited, Digital Presentation) The Discovery and Development of Rechargeable Zn/CuO Batteries

Batteries are easy to use, remotely monitorable, not fuel dependent, easily permitted and installed, and start automatically and reliably during an electrical outage. This makes them optimal for stationary storage and power assurance applications. Within battery-based grid storage, as of mid-2017, lithium-ion, sodium-ion, and lead-acid systems are the leaders, comprising 59% (~1.1 GW), 8% (0.15 GW), and 3% (0.06 GW) of global operational electrochemical storage, respectively.1 However, these batteries suffer from low energy density, high cost, poor safety, environmental concerns, and/or cycle life. Existing battery options on the market also do not meet the required market needs for long-duration backup power. For example, lead-acid batteries require too much space, are heavy, and contain toxic materials. Lithium-ion batteries, while compact and capable of excellent cycle life, are too expensive to serve long outages and have notable flammability and environmental risks.Alkaline zinc-based batteries are a strong candidate for electrical grid storage applications due to zinc’s high capacity (820 mAh/g), established materials supply chain and low cost.1 Alkaline-based cells are generally considered safe and do not have the temperature limitations of Li-ion or Pb-acid batteries, thereby removing the need for complicated thermal management control strategies and providing for simpler systems with lower integration costs. To realize the highest energy density batteries, Zn needs to be coupled with a similarly low cost, abundant and high-capacity cathode. Historically Zn has been paired with MnO2 (616 mAh/g), CuO (674 mAh/g) and S (1675 mAh/g) cathodes to produce energy dense primary batteries. If reversibility can be proven for these conversion cathodes, they would be enticing candidates for grid storage systems.In this presentation, we will report on the development of electrochemically reversible conversion cathodes for alkaline Zn-batteries. Specifically, we will focus on copper oxide-based cathodes and their use in alkaline Zn/CuO batteries with application for large scale grid storage.2 Sandia has recently developed rechargeable alkaline Zn/CuO batteries with very high areal capacities of ~ 40 mAh/cm2 and energy densities of > 200 Wh/L. This is among the highest ever energy density reported for a laboratory scale alkaline Zn–based battery using a conversion cathode. In this example, the rechargeability is enabled by the addition of a bismuth (Bi2O3) additive that facilitates the electrochemical reversibility of Cu2O and Cu(OH)2 species. Data collected from a variety of techniques, including cyclic voltammetry (CV), rotating ring-disk electrode (RRDE) voltammetry, electrochemical impedance spectroscopy (EIS), electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and operando energy-dispersive X-ray diffraction measurements will be presented to elucidate the role of the additive in enabling reversibility in Zn/CuO batteries. In addition, the general challenges of achieving high-capacity Zn anodes and the pairing of two high-capacity conversion electrodes to form the battery, each which cycles through the formation of soluble “-ate” complexes [i.e., cuprate, Cu(OH)4 2- and zincate, Zn(OH)4 2-] will also be covered.The goal is to demonstrate a Zn/CuO battery with long lifetime, at appreciable energy densities (> 200 Wh/L), with excellent safety, lower toxicity and sufficiently low cost to be manufactured and installed on the grid. While these laboratory scale Zn/CuO battery builds have very promising characteristics to date they have not been optimized or adapted for consumer or market-based needs in terms of power performance, energy density, cycle life or stability in terms of shelf life and the ability to tolerate partial state of charge. Progress towards these goals may also be discussed.This work was supported by the U.S. Department of Energy, Office of Electricity, and the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525. The views expressed herein do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

(Invited) Deeply Rechargeable Zinc Anodes for High-Energy Rechargeable Aqueous Batteries

Zinc-based aqueous batteries are promising alternative to many mainstream battery technologies today, due to the superior safety. However, existing zinc anodes suffer from either poor cycle life or low utilization in both neutral and alkaline aqueous electrolytes. Passivation, dissolution, and hydrogen evolution are three main reasons for irreversibility of zinc anodes in alkaline electrolytes, which limits the rechargeability and usable energy density. In this talk, I will present our recent works on using nanoscale material design to overcome passivation, dissolution, and hydrogen evolution issues of zinc anode, towards a deeply rechargeable zinc-based battery. I will also introduce the battery-gas chromatography quantitative analysis, as well as in situ microscopy methodologies we have developed, to quantify gas evolution side reaction, as well as visualize the reaction on electrodes during operation.

(Invited) Sustainability, Safety, Scalability, Rechargeability, and Manufacturability Courtesy of Architected Zinc Anodes

Towards the goal of decarbonizing electrification, concerns remain over the sustainability of the requisite Li and Co, as well as the stringent transportation limits on the amount and operational state of Li allowed in airfreight. Rechargeable zinc-based batteries using aqueous electrolyte offer a compelling alternative to lithium-based batteries with the added benefit of a two-electron anode that augments the energy density, helping to compensate for lower cell voltage inherent to aqueous electrolytes. To solve the standing caveat with rechargeable zinc-based batteries — that they form separator-piercing dendrites — we built on our understanding of the importance of 3D co-continuous wiring of electrons, ion, and molecules in energy-storing nanoarchitectures. Sponge form factors fabricated by fusing ~50 µm zinc particles into a monolithic pore–solid architecture physically prevents formation of dendrites even at high charging current density [1,2]. Throughout the story of the NRL Zn sponge anode, each successive generation of the electrode has been fabricated with manufacturability as a foremost consideration, such that the current sponge formulation (Gen 5) is processed quickly, at scale, to sizes necessary for decarbonizing electrification. I will present the performance of these “big and strong” zinc sponges versus a variety of cathodes and the potential paths forward for the development and transition of this safer energy-storage technology.[1] J.F. Parker, C.N. Chervin, E.S. Nelson, D.R. Rolison, J.W. Long, “Wiring zinc in three dimensions re-writes battery performance―Dendrite-free cycling.” Energy Environ. Sci., 7, 1117–1124 (2014).[2] J.F. Parker, C.N. Chervin, I.R. Pala, M. Machler, M.F. Burz, J.W. Long, and D.R. Rolison, “Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion.” Science, 356, 415–418 (2017).

Methods for Rational Design of Advanced Zn-Based Batteries.

Rechargeable aqueous zinc-based batteries (AZBs) have received massive attention as promising contenders for the future large-scale energy storage due to their low cost, inherent safety, and abundant resources. However, the insufficient energy density and poor stability have become the key to hinder their further application. As is well known, the energy densities (E, Wh kg-1 ) of AZBs are determined by the specific capacity (mAh g-1 ) and output voltage (V). Given the fixed redox potential and capacity of the Zn metal anode, the energy density of AZBs is mainly determined by the cathode material, and the rich material systems of the cathode provide more possibilities to this field. Meanwhile, the methods to improve the stability and performance of the Zn anodes have gained more and more attention due to the severe Zn dendrite growth that can pierce the separator and lead to short-circuiting of the cell. Therefore, in this review, we comprehensively summarize the rational design methods in optimizing the cathode, anode, and device architecture, and classic examples of each catalogue are discussed in details as well. Last, the issues and outlook for further development of high performance AZBs are also presented.

Zinc Anodes Modified by One-Molecular-Thick Self-Assembled Monolayers for Simultaneous Suppression of Side-Reactions and Dendrite-Formation in Aqueous Zinc-Ion Batteries.

Repeated charge/discharge in aqueous zinc-ion batteries (ZIBs) commonly results in surface corrosion/passivation and dendrite formation on zinc anodes, which is a major challenge for the commercialization of zinc-based batteries. In this work, metallic Zn modified by self-assembled monolayers is described as a viable anode for ZIBs. ω-mercaptoundecanoic acid that is spontaneously adsorbed on Zn (MUDA/Zn) contributes to the simultaneous suppression of side reactions and dendrite formation in ZIBs. Though one-molecular-thick, densely packed alkyl chains prohibit H2 O and H+ from making direct contact with the underlying Zn, and surface carboxylate moieties (-COO- ) effectively repel anionic species (OH- ) in a solution, which renders a Zn anode inert against zincate formation within a wide range of pH. In contrast, the electrostatic attraction between surface-carboxylates and cations increases the concentration of Zn2+ on the surface of MUDA/Zn to facilitate Zn plating/stripping with less overpotentials. The high concentration of Zn2+ also results in an increased number of nucleation sites, which enhances the lateral growth of Zn with no formation of dendrites. As a result, MUDA/Zn shows excellent stability during prolonged Zn plating/stripping within a wide range of pH. The advantageous properties of MUDA/Zn are also retained in full-cells coupled with δ-MnO2 cathodes.

Long-Life and Highly Utilized Zinc Anode for Aqueous Batteries Enabled by Electrolyte Additives with Synergistic Effects.

After decades of development, zinc-based batteries with the advantages of high energy density, low cost, and environmental benignity have been considered as a promising battery system in the application of energy storage. However, the poor cycle performance of zinc anode strongly restricts the cycle life of zinc-based batteries and thus limits its large-scale application. Electrolyte additives have been proven to be one of the most straightforward strategies in improving the stability of zinc anode during cycles, while the options of additives are still limited. This work is based on the in-depth investigation of the electrochemical behavior of both the organic additives and the zinc species in the electrolyte. The modification effects of poly(vinyl alcohol) (PVA) and vanillin as two typical additives from the electroplating industry in both the zinc plating and zinc anode are systematically studied. It is revealed that PVA could increase the utilization and rate performance of the anode, while greatly promoting the corrosion and shape change of the zinc anode. On the contrary, the existence of vanillin could maintain the structure of the anode during cycles, while the rate performance of the battery is hindered. With the coaddition of the PVA and vanillin, the zinc anode shows superior performance in cycle life, rate performance, active material utilization, and discharge energy retention. These findings provide insight for the enrichment of electrolyte additives in zinc-based batteries.

Magnetic field stabilizes zinc anode

Zinc-based batteries have high theoretical specific capacity and low production cost, but the formation of Zn dendrites limits its practical application in aqueous batteries. In this work, a new method for Zn dendrite suppression by external magnetic field is proposed. Under the interaction of magnetic field and electric field, Zn ions are affected by Lorentz force and spiral motion, which produces disturbance to the electrolyte and promotes the mass transfer process on the electrode surface. This process promotes the mass transfer process on the electrode surface, makes the distribution of zinc ions more uniform, reduces the concentration polarization, and effectively inhibits the growth of zinc dendrites. The electrochemical performance test results show that the magnetic field effect can effectively reduce the nucleation overpotential of Zn and prolong the cycle life. This new method of Zn dendrite suppression by applying magnetic field to the outside of the cell without modifying the inside of the cell has a very wide range of research and application value.

Sodium Polyacrylate Hydrogel Electrolyte Hybridized with Layered Double Hydroxide for Solid-State NiCo/Zinc Battery

Zinc-based batteries have attracted attention for their safety in aqueous electrolytes with low cost, environmental friendliness, and high capacity. In this study, layered double hydroxide, a solid-state OH− ion conductor, was hybridized with sodium polyacrylate hydrogel to construct a strong elastic hydrogel electrolyte (PANa-LDH) with high OH− ion conductivity. PANa-LDH, KOH was introduced by dipping into 6.0 M KOH solution, showed a significantly high ionic conductivity of 0.213 S cm−1 at 30 °C. A solid-state battery was fabricated using nickel-cobalt hydroxide cathode, PANa-LDH electrolyte, and zinc anode. The high specific capacity of 287 mAh g−1 was obtained at 0.1 A g−1 with high energy and power densities of 212 Wh kg−1 and 73 kW kg−1 (based on the cathode weight), respectively.

Structural regulation strategies towards high performance organic materials for next generation aqueous Zn-based batteries

Environmental degradation has promoted the exploitation of novel energy-storage devices. Electrochemical energy technologies, including supercapacitors and aqueous batteries, are highly desirable for energy storage applications. Among them, aqueous zinc-based batteries (AZBs) are highly valued because of their inherent safety and low cost. One class of emerging materials favorably employed in these devices are organic cathodes, featuring resource renewability, cost-effectiveness, and adjustable electrochemical properties via facile structural modification compared to the conventional inorganic cathodes. To date, various types of organic compounds have been developed and applied to AZBs. This paper comprehensively reviews the mechanisms involved in organic electrode material reactions, highlighting the structural modifications, including morphological, molecular, functional group, crystal, and electronic structures, affecting the final device performance. Conclusively, the prospects of practical applications of zinc/organic aqueous battery are delineated.

Unraveling the mechanism of non-uniform zinc deposition in rechargeable zinc-based batteries with vertical orientation

• The non-uniform zinc deposition in the vertical direction is investigated. • Optical observations and stripping/platting model are combined in this work. • The non-uniform deposited zinc is started by nucleation site fracture. • The inhomogeneity is exacerbated by the non-uniform current and hydrogen evolution. Secondary zinc-based batteries demonstrate a bright prospect as a candidate for next-generation electrochemical energy storage devices. However, the inhomogeneous zinc deposition with vertical orientation during electrochemical stripping/platting cycles leads to battery failure quickly and thereby limits commercial applications of zinc-based batteries. In this work, the deposited electrochemical reaction is deeply investigated and the mechanism of inhomogeneous electrochemical deposition is proposed via in-situ optical observation and numerical analysis. During the deposited reaction, zinc atoms prefer to deposit on the nucleation sites on the electrode surface, changing the morphology of nucleation sites and leading to possible fractures. The fractural zinc fragments then accumulate at the bottom and connect to the bulk electrode, which initiate the inhomogeneous distribution in the vertical direction where the protrusion appears at the bottom, and the middle and top parts have rare deposited zinc. The inhomogeneity is exacerbated during stripping/platting reaction cycles due to the non-uniform local current density distribution on the emerging protrusion. Besides, the generated bubbles caused by hydrogen evolution exacerbate the inhomogeneous distribution via changing the ion distribution. Based on the conclusions, a uniform deposition behavior is achieved via modulating the ion distribution by the flowing electrolyte as a demonstration. The unraveled mechanisms can serve as a reference for the design of advanced zinc-based batteries with stable electrodes.

Structural Regulation of ZnMn2O4 cathode material by K, Fe-Double doping to improve its rate and cycling stabilityfor rechargeable aqueous zinc-based batteries

• The K, Fe double doping strategy for ZnMn 2 O 4 is proposed for the first time. • Oxygen defects are formed by double doping. • K, Fe-ZMO with lower formation energy has better structural stability. • The modification is beneficial to improve the electrical conductivity. • The rate and cycling stability of K, Fe-ZMO is significantly improved. In aqueous zinc-based batteries (ZBBs), manganese-based materials are considered to be potential cathode materials. However, sluggish electrochemical reaction kinetics and problems with manganese dissolution have limited their further development. Herein, K and Fe double-doped ZnMn 2 O 4 (K, Fe-ZMO) is demonstrated to be effective in solving the above problems. The doping of K and Fe can form oxygen defects to enhance the conductivity of the material and the diffusion of Zn 2+ . Interestingly, the K, Fe-doped ZnMn 2 O 4 shows a high specific capacity of 221.2 mA h g −1 (0.1 A g −1 ) after 50 cycles, more than the pure ZnMn 2 O 4 (137.3 mA h g −1 ). The capacity retention (≈88.1% 500 cycles at 1.0 A g −1 ) is also better than ZnMn 2 O 4 cathode (≈27.5% 370 cycles at 1.0 A g −1 ). Density functional theory (DFT) calculations prove that double doping and oxygen defects can facilitate electronic rearrangement to enhance the conductivity, which finally improves the reaction kinetics and electrochemical performance of the K, Fe-ZMO. Furthermore, the modifications can also reduce the formation energy so as to effectively stabilize the Mn-O bond and Fe-O of K, Fe-ZMO, which alleviates the dissolution of manganese. We believe that the strategy proposed in this work will provide another example for the practical application of manganese-based materials in aqueous zinc-based batteries.

A high strength, anti-corrosion and sustainable separator for aqueous zinc-based battery by natural bamboo cellulose

Although aqueous zinc-based batteries (AZBs) have aroused extensive research, there are little studies to develop a separator specifically for AZBs, and the widely used Glass Fiber (GF) has poor mechanical strength, which is difficult to meet the requirements of AZBs. Here, a bamboo cellulose membrane (BCM) with natural nano-scale pores is developed by cellulose nanosheets self-assembled, which can be used as a special separator for AZBs. The hierarchical structure formed by cellulose nanosheets endows BCM with a tensile strength up to 81 MPa, 150 times that of GF, able to well block the penetration of zinc dendrites. The rich natural nano-scale pores in BCM can help to facilitate the homogeneous Zn2+ flux at the surface of zinc anode to achieve uniform deposition. Moreover, BCM shows excellent anti-corrosion properties in a wide pH (3.6–13.6) range. The zinc symmetric cell equipped with BCM exhibits much prolonged cycle life, e.g. up to 5000 h and 5000 h (0.5 mA cm−2 0.5 h) in 3 M Zn(CF3SO3)2 electrolyte and 1 M KOH electrolyte, in contrast to 30 h and 4 h for the cell with conventional GF separator. This work demonstrates that developing special separator is very important for the construction of high-performance AZBs.

Flexible Ti3C2Tx/Nanocellulose Hybrid Film as a Stable Zn-free Anode for Aqueous Hybrid Zn-Li Batteries.

Aqueous zinc-based batteries are a very promising technology in the post-lithium era. However, excess zinc metals are often used, which results in not only making a waste but also lowering the actual energy density. Herein, a Ti3C2Tx/nanocellulose (derived from soybean stalks) hybrid film is prepared by a facile solution casting method and employed as the zinc-free anode for aqueous hybrid Zn-Li batteries. Benefiting from the ultra-low diameter and rich hydroxyl groups of nanocellulose, the hybrid film exhibits better mechanical properties, superior electrolyte wettability, and more importantly, significantly improved zinc plating/stripping reversibility compared to the pure Ti3C2Tx film. The hybrid film also dramatically overwhelms the stainless steel as the electrode for reversible zinc deposition. Further analysis shows that the hybrid film can lower the zinc deposition overpotential and promote the desolvation process of hydrated Zn2+ ions. In addition, it is found that hexagonal Zn thin flakes are horizontally deposited onto the hybrid film owing to the low lattice mismatch between the Ti3C2Tx surface and the (002) facet of Zn. Consequently, zinc dendritic growth and accompanied harmful side reactions can be considerably inhibited by the hybrid film, and the assembled Zn-Li hybrid batteries exhibit excellent electrochemical performances. This work might inspire future work on zinc-based batteries.

Super-resolved dynamics of isolated zinc formation during extremely fast electrochemical deposition/dissolution processes.

The development of zinc-air batteries with high-rate capability and long lifespan is critically important for their practical use, especially in smart grid and electric vehicle application. The formation of isolated zinc (i-Zn) on the zinc anode surface, however, could easily lead to deteriorated performance, such as rapid capacity decay. In particular, under the fast charging/discharging conditions, the electrochemical activities on the anode surface are complicated and severely suppressed. Thus, it is highly desirable to deeply understand the formation mechanism of i-Zn and its relationship with the electrochemical performance during extremely high-rate cycling. Herein, we employed a super-resolution dark-field microscope to in situ analyze the evolution dynamics of the electrolyte-Zn interface during the extremely fast electrochemical deposition/dissolution processes. The unique phenomenon of nanoscopic i-Zn generation under the condition is unveiled. We discovered that the rapid conversion of nanoscopic i-Zn fragments into passivated products could greatly exacerbate the concentration polarization process and increase the overpotential. In addition, the role of large-sized i-Zn fragments in reducing the coulombic efficiency is further elucidated. This information could aid the rational design of highly effective anodes for extremely high-rate zinc-based batteries and other battery systems.

Regulating zinc metal anodesvianovel electrolytes in rechargeable zinc-based batteries

This review summarizes the latest strategies of advanced electrolyte engineering to construct a stable zinc metal anode in rechargeable zinc batteries.

A strategy for anode modification for future zinc-based battery application.

In the past several years, rechargeable zinc batteries, featuring the merits of low cost, environmental friendliness, easy manufacturing, and enhanced safety, have, attracted much attention. Zinc (Zn) anodes for zinc metal batteries play an important role. In this review, the fundamental understanding of these batteries and modification strategies to deal with the problematic issues for Zn anodes, including dendrite growth, corrosion, and the hydrogen evolution phenomenon will be summarized. The practical application of Zn anodes can still lead to Zn dendrites, various side reactions, and serious safety risks. Therefore, metal-free anodes for "rocking chair" zinc ion batteries to replace Zn anodes are systemically reviewed. The performance and the zinc storage mechanism of metal-free anodes will be discussed. Subsequently, a "rocking chair" zinc ion battery prototype selected as a recent example is assessed to explore the merits and demerits of Zn anodes and metal-free anodes. To conclude, a perspective on the future of zinc metal batteries and "rocking chair" zinc ion batteries is presented. It is hoped that this review may provide for further improvement of commercial rechargeable zinc batteries.

Opportunities for biocompatible and safe zinc-based batteries

This review presents the recent progress and research potential of biocompatible ZBs for wearable and implantable devices. Challenges and solutions have been discussed for future investigations, followed by roadmaps towards biocompatibility.

Potential-Dependent Passivation of Zinc Metal in a Sulfate-Based Aqueous Electrolyte.

Owing to its abundance, high theoretical capacity, and low electrode potential, zinc is one of the most important metallic anodes for primary and secondary batteries such as alkaline and zinc-air batteries. In the operation of zinc-based batteries, passivation of the anode surface plays an essential role because the electrode potential of zinc is slightly below that of the hydrogen evolution reaction. Therefore, it is important to scrutinize the nature of the passivation film to achieve anticorrosion inside batteries. Herein, the potential-dependent formation and removal of the passivation film during the deposition and dissolution of zinc metal in aqueous electrolytes are detected via electrochemical quartz crystal microbalance analysis. Film formation was not noticeable in hydroxide-based electrolytes; however, sulfate-based electrolytes induced potential-dependent formation and removal of the passivation film, enabling a superior coulombic efficiency of 99.37% and significantly reducing the rate of corrosion of the zinc-metal anodes. These observations provide insights into the development of advanced electrolytes for safe and stable energy-storage devices based on zinc-metal anodes.

Silver Nanoparticles Guide Uniform Zn Nucleation in the Porous Carbon Skeleton for Dendrite-Free Zinc Metal Anodes

Aqueous zinc-based batteries have been proposed as one of the most promising electrical energy-storage systems owing to their unique advantages of low potential, high theoretical capacity, intrinsic safety, low cost and high ionic conductivity. Despite the current progress in the exploration of the cathode (including NiOOH, MnO2, air cathode, etc.) and electrolyte (neutral ZnSO4, Zn(otf)2, “water in salt”, etc.), the practical implementation of zinc-based battery is still largely impeded by the poor cycle life of Zn metal anode due to the formation of dendrites. One attractive strategy is employing three-dimensional (3D) porous metrics as a host for Zn metal. Among the various 3D hosts, carbon-based materials with lightweight properties, chemical stability and low cost are more attractive. However, due to the high electronic conductivity and overpotential of carbon materials to Zn, the Zn is inclined to plate on the surface of carbon skeletons rather than throughout the whole host materials, which limits the effectiveness of the 3D structural design. Here, we prepared Ag nanoparticles anchored on the 3D porous carbon matrix host (Ag-GS/CNT) by freeze-drying and in situ reduction methods. The uniformly distributed Ag nanoparticles with a lower Zn nucleation barrier compared to carbon guide the Zn deposition within the pores of the 3D hosts. The 3D porous carbon host materials with a large active surface can minimize the local current density and suppress dendrite growth. besides, confining the Zn metal within the host effectively restricts the huge volume change, improving the stability of Zn metal anode upon repeated cycles. Both the Zn–air battery and Zn-ion battery based on Ag-GS/CNT//Zn anode display superior electrochemical performance.

Electrolyte additives inhibit the surface reaction of aqueous sodium/zinc battery

In aqueous zinc-based batteries, the reaction by-product Zn4SO4(OH)6·xH2O is commonly observed when cycling vanadium-based and manganese-based cathodes. This by-product obstructs ion transport paths, resulting in enhanced electrochemical impedance. In this work, we report a hybrid aqueous battery based on a Na0.44MnO2 cathode and a metallic zinc foil anode. The surfactant sodium lauryl sulfate is added to the electrolyte as a modifier, and the performance before and after modification is compared. The results show that sodium lauryl sulfate can generate an artificial passivation film on the electrode surface. This passivation film reduces the generation of Zn4SO4(OH)6·xH2O and inhibits the dissolution of Na0.44MnO2 in the electrolyte. Therefore, the reaction kinetics and cycle stability of the battery are significantly enhanced. A battery with this electrolyte additive delivers an initial discharge capacity of 235 mA h g−1 at a current density of 0.1 A g -1. At the same time, the battery has excellent rate performance. Under the high-rate condition of 1 A g−1, the battery still maintains a capacity retention rate of 93% after 1500 cycles. Finally, the functional mechanism of by-product inhibition by the electrolyte additive is discussed.