Boosting high-loading zinc-ion battery performance: Zn-Doped δ-MnO2 cathodes to promote Zn2+ storage

With the development of science and technology, now the comprehensive use of electronic equipment, has led to the increasing demand for energy storage systems. The market requires high-performance energy storage systems, zinc-ion batteries have the merits of good energy storage performance, low cost, and high safety, thus arousing extensive attention. Because of the diversity of the environment on the earth, the aqueous zinc ion batteries should meet the requirement of sustainability and feasibility working in wide temperature environments. How to ensure that zinc-ion batteries can work in such a harsh environment has become a research topic nowadays. As the ambient temperature decreases, the energy storage performance decays, including greatly reduced cycling life, increased resistance, and inferior charge/discharge performance. Especially below zero, the electrolyte may be frozen. Therefore, the application of aqueous zinc-ion batteries in these low-temperature environments has become a further research direction. To enhance the low-temperature performance of zinc-ion batteries, many strategies have been developed, such as improving the performance of the positive and negative electrodes, optimizing the electrolyte material, and developing separators. Among them, optimizing the electrolyte is the most effective strategy. Electrolyte is an important part of the battery, which contacts with the positive and negative stages of the battery and produces chemical reactions to produce electricity. In the process of charge and discharge, the electrolyte is mainly used for mass transportation, so the electrolyte is particularly important for enhancing low-temperature performance for zinc-ion batteries. Correspondingly, many researchers focus on designing and synthesizing advanced electrolytes. This paper summarizes the state-of-art development of low-temperature zinc-ion batteries domestically and internationally and classifies and analyzes the solid, liquid, and gel electrolytes.

With the continuous development of science and technology, battery storage systems for clean energy have become crucial for global economic transformation. Among various rechargeable batteries, lithium-ion batteries are widely used, but face issues like limited resources, high costs, and safety concerns. In contrast, zinc-ion batteries, as a complement to lithium-ion batteries, are drawing increasing attention. In the exploration of zinc-ion batteries, especially of phosphate-based cathodes, the battery action mechanism has a profound impact on the battery performance. In this paper, we first review the interaction mechanism of multi-ion, dual-ion, and single-ion water zinc batteries. Then, the impact of the above mechanisms on battery performance was discussed. Finally, the application prospects of the effective use of multi-ion, dual-ion, and single-ion intercalation technology in zinc-ion batteries is reviewed, which has significance for guiding the development of rechargeable water zinc-ion batteries in the future.

PurposeAqueous zinc-ion battery has broad application prospects in smart grid energy storage, power tools and other fields. Co3O4 is one of the ideal cathode materials for water zinc-ion batteries due to their high theoretical capacity, simple synthesis, low cost and environmental friendliness. Many studies were concentrated on the synthesis, design and doping of cathodes, but the effect of process parameters on morphology and performance was rarely reported.Design/methodology/approachHerein, Co3O4 cathode material based on carbon cloth (Co3O4/CC) was prepared by different temperatures hydrothermal synthesis method. The temperatures of hydrothermal reaction are 100°C, 120°C, 130°C and 140°C, respectively. The influence of temperatures on the microstructures of the cathodes and electrochemical performance of zinc ion batteries were investigated by X-ray diffraction analysis, scanning electron microscopy, cyclic voltammetry curve, electrochemical charging and discharging behavior and electrochemical impedance spectroscopy test.FindingsThe results show that the Co3O4/CC material synthesized at 120°C has good performance. Co3O4/CC nanowire has a uniform distribution, regular surface and small size on carbon cloth. The zinc-ion battery has excellent rate performance and low reaction resistance. In the voltage range of 0.01–2.2 V, when the current density is 1 A/g, the specific capacity of the battery is 108.2 mAh/g for the first discharge and the specific capacity of the battery is 142.6 mAh/g after 60 charge and discharge cycles.Originality/valueThe study aims to investigate the effect of process parameters on the performance of zinc-ion batteries systematically and optimized applicable reaction temperature.

Rechargeable aqueous zinc ion batteries are currently receiving much attention as large-scale energy storage systems due to their inherent safety, fast ion kinetics, low cost materials and environmental friendliness. Considering the recent literature, the state-of-the-art zinc ion battery combines a manganese oxide cathode, a planar zinc foil anode and an aqueous, mildly acidic electrolyte [1]. Even though the corresponding electrochemical models are subject to recent discussions [2] it is possible to derive basic kinetic parameters allowing a further development of the cell design and electrode composition. For this purpose in this study, zinc foil is used as the anode, a slightly acidic zinc sulphate solution as electrolyte and a stainless steel foil coated with manganese dioxide as the cathode. The coating process of the cathode may greatly influence the kinetics of the battery due to the fact that the cathode thickness, the porosity and the particle size are decisive for the overall performance of the battery. The cathode slurry is a mixture of manganese dioxide, carbon black, binder and distilled water. Previous studies showed that particularly the particle size of the manganese oxide in the cathode has great influence on the capacity of the battery [3]. In order to understand the kinetics of the coated cathode it was investigated if the electrochemical process is mass or charge transfer controlled and corresponding parameters of the Butler-Volmer equation are determined by electrochemical characterization of the samples. These kinetic parameters are identified in order to implement a simulation model allowing a further optimization of the battery cell architecture and the required electrode properties. References Liu, J.; Xu, C.; Chen, Z.; Ni, S.; Shen, Z.X. Progress in aqueous rechargeable batteries. Green Energy & Environment 2018, 3, 20–41, doi:10.1016/j.gee.2017.10.001.Song, M.; Tan, H.; Chao, D.; Fan, H.J. Recent Advances in Zn-Ion Batteries. Adv. Funct. Mater. 2018, 28, 1802564, doi:10.1002/adfm.201802564.Bischoff, C.; Fitz, O.; Schiller, C.; Gentischer, H.; Biro, D.; Henning, H.-M. Investigating the Impact of Particle Size on the Performance and Internal Resistance of Aqueous Zinc Ion Batteries with a Manganese Sesquioxide Cathode. Batteries 2018, 4, 44, doi:10.3390/batteries4030044.

Zinc has been regarded as a promising anode material for aqueous batteries in view of its advantages including high specific capacity, abundance and intrinsic safety. Aqueous zinc ion batteries have attracted growing attention as a potential alternative to lithium ion batteries, especially for medium and large-scale energy storage. Aqueous zinc ion batteries consist of a zinc anode and a zinc intercalating cathode in a zinc-salt-containing electrolyte and use zinc ions as charge carriers. The electrolyte transporting zinc ions between the anode and the cathode plays an essential role in determining battery performance and life. Visualising ion transport in the electrolytes of zinc ion batteries can give insights into electrolyte dynamics as well as battery processes. Yet, this is limited by the spatial-temporal resolution of the existing techniques. Moreover, most of the existing in-situ visualisation techniques are very expensive and not easily accessible. Fluorescence microscopy provides a powerful tool for probing tiny structures and tracking species in real time. It relies on fluorescence which occurs when molecules absorb light with a certain wavelength followed by the re-emission of light with a longer wavelength. These excitation and emission wavelengths are usually unique fingerprints of certain substances. Fluorescent sensors, with high sensitivity of fluorescence assays, have been widely exploited as a useful tool for species detection and mechanistic studies in biology and chemistry. In this study, a novel microfluidics-based fluorescence microscopy platform is developed for visualising and characterising zinc ion transport in the electrolytes of zinc ion batteries. The platform is calibrated by comparing the measurement results with the literature data. Key transport properties of zinc ions are quantified under different electrolyte conditions. The developed platform is demonstrated to be a simple and versatile tool for electrolyte characterisation, which provides key information guiding future electrolyte development and battery performance improvement.

Aqueous zinc ion batteries are a very promisingly emerging class of energy storage devices. They are brought to the attention of the researchers owing to the abundant resourcefulness, user and environmental friendliness, and excellent water compatibility unlike the alkaline and alkaline earth metals. Unfortunately, their research and development are still in the unmatured stage. Few of the inorganic materials, such as oxides of manganese, vanadium, Prussian blue, etc., are some of the inorganic materials evaluated as cathode for zinc batteries. Even though inorganic materials offer high energy density which directly affects the size of the battery, they face some serious constraints of being used for real practical applications. They undergo irreversible structural lattice changes during the cycling process which ultimately deteriorate the battery performance over prolonged cycling. In addition, they face serious dissolution problems, lack of resourcefulness, and environmental non-benignity. In this regard, organic cathodes are interesting candidates because of their flexibility, simple charge storage mechanism, numerous choices of molecular engineering, and high resourcefulness. Herein, we studied the anthraquinone derivative as an organic cathode in ionic liquid electrolytes. Even though aqueous electrolytes are user-friendly, excessive water evaporation occurs with subsequent salt crystallization on the electrode which deteriorates the battery performance. We previously reported on addressing the restriction of water evaporation by choosing ethylene glycol as an electrolyte additive. Since ionic liquid exists as a liquid at room temperature, we selected different types of ILs, ie., imidazole containing different types of alkyl and functionalized alkyl chains as shown in the figure.This work essentially emphasizes the aqueous zinc battery performance using functionalized ionic liquids as electrolytes with a newly designed anthraquinone-based organic cathode. It has been observed that the zwitterionic electrolyte exhibited comparatively good capacity performance of 156.2 mAhg-1 at 50 mAg-1 current density. The cycling stability, as well as coulombic efficiency, were also found to be much promising. On the whole, user-friendly organic-based electrolyte, as well as organic cathode, converge a new integrated electrode-electrolyte system for zinc ion battery. The detailed battery performance and post-mortem analysis have also been performed which reinvigorate the battery research, for zinc-like multivalent ion-based batteries in particular. Figure 1

Unravelling the proton hysteresis mechanism in vacancy modified vanadium oxides for High-Performance aqueous zinc ion battery

Currently, aqueous zinc-ion batteries, with large reserves of zinc metal and maturity of production, are a promising alternative to sustainable energy storage. Nevertheless, aqueous solution has poor frost resistance and is prone to side reactions. In addition, zinc dendrites also limit the performance of zinc-ion batteries. Biomass, with complex molecular structure and abundant functional groups, makes it have great application prospects. In this review, the research progress of biomass and its derived materials used in zinc-ion batteries are reviewed. The different regulation strategies and characteristics of biomass used in zinc-ion battery electrodes, electrolyte separators and binders are demonstrated. The regulation mechanism is analyzed. At the end, the development prospect and challenges of biomass in energy materials application are proposed.

Zinc-ion batteries are one of the promising energy storage devices, which have the advantages of environmental friendliness, high safety and low price and are expected to be used in large-scale battery application fields. However, four prominent water-induced adverse reactions, including zinc dendrite formation, zinc corrosion, passivation and the hydrogen evolution reaction in aqueous systems, seriously shorten the cycling life of zinc-ion batteries and greatly hinder their development. Based on this, polymer gel electrolytes have been developed to alleviate these issues due to their unique network structure, which can reduce water activity and suppress water-induced side reactions. Based on the challenges of polymer gel electrolytes, this review systematically summarizes the latest research progress in the use of additives in them and explores new perspectives in response to the existing problems with polymer electrolytes. In order to expand the performance of polymer gel electrolytes in zinc-ion batteries, a range of different types of additives are added via physical/chemical crosslinking, such as organic or inorganic substances, natural plants, etc. In addition, different types of additives and polymerization crosslinking from different angles essentially improve the ionic conductivity of the gel electrolyte, inhibit the growth of zinc dendrites, and reduce hydrogen evolution and oxygen-absorbed corrosion. After these modifications of polymer gel electrolytes, a more stable and superior electrochemical performance of zinc-ion batteries can be obtained, which provides some strategies for solid-state zinc-ion batteries.

Aqueous zinc-ion batteries (ZIBs) employing zinc metal anodes are gaining traction as batteries for moderate to long duration energy storage at scale. While ZIBs with near-neutral pH electrolytes are attractive for safety reasons, corrosion of the zinc metal anode through reaction with water limits battery efficiency. Much research in the past few years has focused on additives that decrease hydrogen evolution, but the precise mechanisms by which this takes place are often understudied and remain unclear. In this work, we study the role of an acetonitrile antisolvent additive in improving the performance of aqueous ZnSO4 electrolytes using experimental and computational techniques. First, results of several electronic and vibrational techniques show that, contrary to previous reports, ACN never displaces water in the first solvation shell of the [Zn(H2O)6]2+ ion and only acts as an anti-solvent in the highly-charged, hydrophilic ZnSO4 solution. Instead, double-layer capacitance measurements and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) experiments indicate that, rather than modifying bulk solvation, acetonitrile modifies the interfacial chemistry, likely by adsorbing onto the electrode surface, resulting in modified Zn deposition and HER kinetics. The interfacial adsorption of acetonitrile then impacts the evolution of deposit morphology over subsequent cycles by modifying zinc nucleation and slowing the ZHS formation rate, as demonstrated using scanning electron microscopy (SEM) imaging and elemental analysis (energy-dispersive spectroscopy, EDS) of copper working electrodes extracted after half-cell cycling experiments. Collectively, this work demonstrates the effectiveness of solvent additive systems in battery performance and durability and provides a new framework for future efforts to optimize ion transport and performance in ZIBs. Reference:1. S.Ilic; M. J. Counihan; S. N. Lavan; Y. Yang; Y. Jiang; D. Dhakal; J. Mars; E. N. Antonio; L. Kitsu Iglesias; T. T. Fister; Y. Zhang; E. J. Maginn; M. F. Toney; R. F. Klie; J. G. Connell, S. Tepavcevic; Role of Antisolvent Additives in Aqueous Zinc Sulfate Electrolytes for Zinc Metal Anodes: The Case of Acetonitrile, ACS Energy Lett., 2024, 9(1), 201-208 DOI:10.1021/acsenergylett.3c02504___________________The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan

This mini‐review comprehensively outlines the latest advancements in protecting zinc anodes in zinc‐ion batteries (ZIBs) through chelation mechanisms. Chelation involves the coordination of ligands with Zn2+, offering promising strategies to address challenges such as dendrite formation and hydrogen evolution reactions. However, there is a lack of comprehensive and unified evaluation of chelation‘s protective effect on the zinc anode, which hinders a thorough assessment of chelation‘s effectiveness. Recent studies have demonstrated the excellent protective performance of chelation in altering solvation structures, modifying SEI structures, and selectively adsorbing species on the zinc anode. Furthermore, while chelation demonstrates significant benefits for the zinc anode, its impact on cathode materials must also be considered. Proper selection of chelation strengths and compatible cathode materials is essential for overall battery performance. Future research directions include exploring the effects of different ligands and coordination numbers on battery performance and extending chelation strategies to other secondary metal batteries. Understanding and optimizing chelation mechanisms are critical for advancing the development of high‐performance ZIBs and other metal‐ion battery technologies.

Zinc corrosion, hydrogen evolution reaction, uneven deposition, and dendrite growth on the zinc anodes are the key factors restraining the electrochemical performance and cycling stability of the aqueous zinc-ion batteries. In this study, learned from the synial membrane, a tiny amount of natural amino acid β-alanine (β-Ala, 0.089 wt %) was introduced as the additive in ZnSO4 electrolyte for strengthening the kinetics of the zinc anode as well as enhancing the performance of zinc ions batteries. A number of modern surface techniques and surface electrochemical analyses were employed to reveal the fundamental reasons for the strengthened zinc anode by β-Ala in ZnSO4 electrolyte. The results show that β-Ala could be adsorbed on zinc electrode surface through intermolecular chelation, which might regulate the chemical environments of the electrolyte and promote uniform deposition of zinc ions. Hence, the β-Ala adsorption film on zinc electrode could suppress the hydrogen evolution reaction and the formation of zinc dendrites, thereby significantly improving the deposition/stripping process of the zinc anode. In particular, the strong hydrogen bonding could restrain the migration of H2O molecules approaching the zinc anode surface, preventing the invasion of water to the zinc electrode surface. Therefore, the addition of dilute β-Ala in the ZnSO4 electrolyte might remarkably prolong the life span of Zn||Zn symmetric batteries to 5000 h under 1 mA cm-2 and 1 mAh cm-2, and to 450 h under 5 mA cm-2 and 3 mAh cm-2 at 298 K, which is much longer than the zinc-zinc symmetric cells including the bare ZnSO4 electrolyte (only 95 h at 5 mA cm-2 and 3 mAh cm-2, and 200 h at 1 mA cm-2 and 1 mAh cm-2). Furthermore, β-Ala was found to significantly improve the cycling stability of Zn||Cu asymmetric cells and Zn||V2O5 full cells. This study provides an effective method for engineering electrolytes to inspire rechargeable zinc-ion batteries by selecting ideal natural biomolecules as the electrolyte additives.

Zinc-ion batteries (ZIBs) are emerging as promising contenders in the realm of energy storage due to their potential for cost-effectiveness, environmental sustainability, high safety. However, the formation of dendrites on Zn anodes, alongside hydrogen evolution and side reactions, represent notable disadvantages in the performance of zinc-ion batteries. These challenges hinder their long-term stability and efficiency, necessitating further research and development efforts to overcome them. Strategies to overcome challenges in zinc-ion batteries include improving Zn anode construction to mitigate dendrite formation and adjusting electrolyte composition to suppress hydrogen evolution and side reactions. Additionally, the use of solid-state or gel polymer electrolytes can enhance ion transport and reduce dendrite formation.In this presentation, we introduce a rapid and effective method for constructing a dual cross-link hydrogel directly onto current collectors, such as Carbon Fiber Paper (CFP) and Carbon Nanotube (CNT) film, utilizing polyacrylamide and aramid nano fiber (ANF). The resulting hydrogel exhibits high ionic conductivity and improved mechanical properties, mitigating the formation of Zn dendrites and enhancing cycling stability in Zn/Zn symmetric cells (stable after 1000 hours of plating/stripping). Additionally, in-situ polymerization on cathode current collectors enhances electrolyte-cathode active material contact, particularly beneficial for porous cathodes like CFP. Furthermore, combined with in-situ electrochemical deposition of MnO2 active material, this approach facilitates the production of practical winding batteries using conventional winding machines. This research provides an efficient approach to assembling practical, flexible and stable AZIBs pouch cells with high capacity and cycling stability.

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