Zinc Sulfur Research Articles

Ionic Covalent Organic Framework Membrane as Active Separator for Highly Reversible Zinc-Sulfur Battery.

Zinc-sulfur (Zn-S) batteries exhibit a high theoretical energy density, nontoxicity, and cost-effectiveness, demonstrating significant potential for integration into large-scale energy storage systems. However, the phenomenon of polysulfide (including dissolved S8 and Sx2-) shuttling is a major issue that results in rapid capacity decay and a short lifespan, limiting the practical performance of sulfur-based batteries. Herein, we fabricated an ionic covalent organic framework (iCOF) membrane as an active separator for the Zn-S battery. Sulfonic acid groups were introduced to the COF membrane, providing abundant negative charge sites in its pore wall. By combining size sieving and charge interaction between the polysulfide and pore wall, the iCOF membrane inhibited the crossover of polysulfides to the Zn metal anode without affecting the transport of metal ions. The Zn-S battery with the iCOF membrane as the separator shows a high-performance and low attenuation rate of 0.05% per cycle over 300 cycles at 2.5 A g-1. This study emphasizes the significance of separator design in enhancing Zn-S batteries and showcases the potential of functionalized framework materials for the development of high-performance energy storage systems.

Recent Progress on Rechargeable Zn-X (X=S, Se, Te, I2, Br2) Batteries.

Recently, aqueous Zn-X (X=S, Se, Te, I2, Br2) batteries (ZXBs) have attracted extensive attention in large-scale energy storage techniques due to their ultrahigh theoretical capacity and environmental friendliness. To date, despite tremendous research efforts, achieving high energy density in ZXBs remains challenging and requires a synergy of multiple factors including cathode materials, reaction mechanisms, electrodes and electrolytes. In this review, we comprehensively summarize the various reaction conversion mechanism of zinc-sulfur (Zn-S) batteries, zinc-selenium (Zn-Se) batteries, zinc-tellurium (Zn-Te) batteries, zinc-iodine (Zn-I2) batteries, and zinc-bromine (Zn-Br2) batteries, along with recent important progress in the design and electrolyte of advanced cathode (S, Se, Te, I2, Br2) materials. Additionally, we investigate the fundamental questions of ZXBs and highlight the correlation between electrolyte design and battery performance. This review will stimulate an in-deep understanding of ZXBs and guide the design of conversion batteries.

Internal Electron Donor Accelerated Sulfur Redox for Aqueous Zn─S Batteries

AbstractImproving the electrical conductivity of sulfur cathode while ensuring its high affinity to catalyst holds the key to facilitate the reaction kinetics of aqueous zinc–sulfur batteries. Herein, the sulfur redox in aqueous electrolyte is accelerated by introducing selenium–sulfur bonds into the sulfur structure to build an internal electron transport path. The Se with less electronegativity can act as an electron donor to accelerate the binding between S and Zn2+. Meanwhile, the bonded Se in the electron‐poor state endows the modified sulfur cathode with a strong affinity to the I3− catalyst, which further facilitates the conversion efficiency. Thus, the internal electron donor assisted sulfur cathode delivers excellent electrochemical performance in terms of high reversible capacity (1490 mAh g−1 at 0.5 A g−1), competitive rate performance (1010 mAh g−1 at 4 A g−1), as well as outstanding cycle stability (735 mAh g−1 at 4 A g−1 after 500 cycles).

Controllable Synthesis of Sub‐10 nm ZnS Nanograins Confined in Micro‐Size Carbon Skeleton for Aqueous Zn–S Batteries

AbstractAqueous zinc–sulfur battery (AZSB) is a promising technology for energy storage, but its practical application is severely limited by the sluggish redox kinetics and large volume expansion of the sulfur cathode. Herein, the controllable synthesis of sub‐10 nm ZnS nanograins confined in micro‐size carbon skeleton (MN‐ZnS/C─H) and its application as the cathode for AZSB is reported. It is revealed that the carbon source, polyvinylpyrrolidone (PVP), can weakly coordinate with Zn2+ and provide a physical confinement for inhibiting the agglomeration of ZnS nanograins during the calcination process. Moreover, the particle size of ZnS (from sub‐10 to 350 nm) and the shape of ZnS/carbon composite (from bulk to sphere) can be well controlled by tuning the chain length of PVP. In the unique hierarchical structure, the ZnS nanograins can provide an optimized ion transmission path, and the micro‐size carbon network not only ensures high electronic conductivity but also maintains structure integrity upon volume variation, endowing the MN‐ZnS/C─H electrode with a high reversible capacity of 370 mA h g−1 at 0.2 A g−1, high rate capability of 209 mA h g−1 at 4 A g−1, and a long lifespan of 210 cycles with 93.2% capacity retention at 2 A g−1.

Trace Selenium Doping for Improving the Reaction Kinetics of ZnS Cathode for Aqueous Zn-S Batteries.

Aqueous Zinc-sulfur (Zn-S) batteries are promising for the field of energy storage due to their low cost, high theoretical capacity, and safety. However, the large volume expansion and the inherently poor conductivity of sulfur would result in electrode cracking and sluggish reaction kinetics, limiting the practical application of Zn-S batteries. Herein, commercial zinc sulfide (ZnS) is employed instead of S as cathode and proposed a doping modification strategy to solve the above problems. The designed ZnS0.93Se0.07 cathode shows good cycle stability and much-improved reaction kinetics, which is due to the smaller bandgap of ZnS0.93Se0.07 (1.40eV) compared to ZnS (1.86eV). As a result, the obtained ZnS0.93Se0.07 cathode exhibits a high specific capacity of 552 mAh g-1 (1672.6 mAh g-1 based on S) at 0.1 A g-1 and 330 mAh g-1 (1000 mAh g-1 based on S) at 2 A g-1. Moreover, the ZnS0.93Se0.07 cathode can provide a high areal capacity of 3.8 mAh cm-2 at a high mass loading of 10mg cm-2 and limited electrolyte (4µL mg-1). This work provides a simple and effective cathode modification strategy, which is conducive to promoting the practical application of Zn-S batteries.

A Tellurium-Boosted High-Areal-Capacity Zinc-Sulfur Battery.

Aqueous rechargeable zinc-sulfur (Zn-S) batteries are a promising, cost-effective, and high-capacity energy storage technology. Still, they are challenged by the poor reversibility of S cathodes, sluggish redox kinetics, low S utilization, and unsatisfactory areal capacity. This work develops a facile strategy to achieve an appealing high-areal-capacity (above 5mAhcm-2) Zn-S battery by molecular-level regulation between S and high-electrical-conductivity tellurium (Te). The incorporation of Te as a dopant allows for manipulation of the Zn-S electrochemistry, resulting in accelerated redox conversion, and enhanced S utilization. Meanwhile, accompanied by the S-ZnS conversion, Te is converted to zinc telluride during the discharge process, as revealed by ex-situ characterizations. This additional redox reaction contributes to the S cathode's total excellent discharge capacity. With this unique cathode structure design, the carbon-confined TeS cathode (denoted as Te1S7/C) delivers a high reversible capacity of 1335.0mAhg-1 at 0.1Ag-1 with a mass loading of 4.22mgcm-2, corresponding to a remarkable areal capacity of 5.64mAhcm-2. Notably, a hybrid electrolyte design uplifts discharge plateau, reduces overpotential, suppresses Zn dendrites growth, and extends the calendar life of Zn-Te1S7 batteries. This study provides a rational S cathode structure to realize high-capacity Zn-S batteries for practical applications.

Evaluating the role of nitrogen in carbon hosts for aqueous zinc sulfur batteries

Evaluating the role of nitrogen in carbon hosts for aqueous zinc sulfur batteries

Advances in Aqueous Zinc Ion Batteries based on Conversion Mechanism: Challenges, Strategies, and Prospects.

Recently, aqueous zinc-ion batteries with conversion mechanisms have received wide attention in energy storage systems on account of excellent specific capacity, high power density, and energy density. Unfortunately, some characteristics of cathode material, zinc anode, and electrolyte still limit the development of aqueous zinc-ion batteries possessing conversion mechanism. Consequently, this paper provides a detailed summary of the development for numerous aqueous zinc-based batteries: zinc-sulfur (Zn-S) batteries, zinc-selenium (Zn-Se) batteries, zinc-tellurium (Zn-Te) batteries, zinc-iodine (Zn-I2) batteries, and zinc-bromine (Zn-Br2) batteries. Meanwhile, the reaction conversion mechanism of zinc-based batteries with conversion mechanism and the research progress in the investigation of composite cathode, zinc anode materials, and selection of electrolytes are systematically introduced. Finally, this review comprehensively describes the prospects and outlook of aqueous zinc-ion batteries with conversion mechanism, aiming to promote the rapid development of aqueous zinc-based batteries.

Facilitating the Electrochemical Oxidation of ZnS through Iodide Catalysis for Aqueous Zinc-Sulfur Batteries.

Aqueous zinc-sulfur (Zn-S) batteries show great potential for unlocking high energy and safety aqueous batteries. Yet, the sluggish kinetic and poor redox reversibility of the sulfur conversion reaction in aqueous solution challenge the development of Zn-S batteries. Here, we fabricate a high-performance Zn-S battery using highly water-soluble ZnI2 as an effective catalyst. In situ experimental characterizations and theoretical calculations reveal that the strong interaction between I- and the ZnS nanoparticles (discharge product) leads to the atomic rearrangement of ZnS, weakening the Zn-S bonding, and thus facilitating the electrochemical oxidation reaction of ZnS to S. The aqueous Zn-S battery exhibited a high energy density of 742 Wh kg(sulfur) -1 at the power density of 210.8 W kg(sulfur) -1 and good cycling stability over 550 cycles. Our findings provide new insights about the iodide catalytic effect for cathode conversion reaction in Zn-S batteries, which is conducive to promoting the future development of high-performance aqueous batteries.

Facilitating the Electrochemical Oxidation of ZnS through Iodide Catalysis for Aqueous Zinc‐Sulfur Batteries

AbstractAqueous zinc‐sulfur (Zn‐S) batteries show great potential for unlocking high energy and safety aqueous batteries. Yet, the sluggish kinetic and poor redox reversibility of the sulfur conversion reaction in aqueous solution challenge the development of Zn‐S batteries. Here, we fabricate a high‐performance Zn‐S battery using highly water‐soluble ZnI2 as an effective catalyst. In situ experimental characterizations and theoretical calculations reveal that the strong interaction between I− and the ZnS nanoparticles (discharge product) leads to the atomic rearrangement of ZnS, weakening the Zn‐S bonding, and thus facilitating the electrochemical oxidation reaction of ZnS to S. The aqueous Zn‐S battery exhibited a high energy density of 742 Wh kg(sulfur)−1 at the power density of 210.8 W kg(sulfur)−1 and good cycling stability over 550 cycles. Our findings provide new insights about the iodide catalytic effect for cathode conversion reaction in Zn‐S batteries, which is conducive to promoting the future development of high‐performance aqueous batteries.

Modulating electrolyte solvation for high-performance aqueous zinc–sulfur batteries

The designed dimethylacetamide-based hybrid electrolyte exhibits 2.5 times lower zinc corrosion and improved sulfur cathode wettability, thus enabling a high-performance aqueous Zn/S battery.

Investigating the impact of mesoporous and microporous carbon host materials on the performance of sulfur cathodes in Zinc-Sulfur batteries

The zinc-sulfur (Zn-S) batteries have attracted extensive research due to its high energy density and safety. However, numerous research focus has focused on optimizing the aqueous electrolyte, the effect of different confinement effects of carbon pores on sulfur on batteries is unclear. In this work, the effects of mesoporous and microporous hosts on electrochemical performance were investigated in detail. The microporous carbon structure provides higher confinement ability for sulfur compared to mesoporous carbon. Ex-situ XRD, EDS mapping, and XPS Ar ion etching techniques were utilized to analyze the factors contributing to the capacity decay of sulfur cathode materials. The insights gained from this study will not only enhance our understanding of the electrochemical behavior of Zn-S batteries, but also provide potential strategies for improving their performance.

High Energy Density Aqueous Zinc–Chalcogen (S, Se, Te) Batteries: Recent Progress, Challenges, and Perspective

AbstractZinc‐ion batteries with chalcogen‐based (S, Se, Te) cathodes have emerged as a promising candidate for utility‐scale energy storage systems and portable electronics, which have attracted rapid attention and offer tremendous opportunities owing to their excellent energy density, on top of the advantages of aqueous Zn batteries including cost‐effectiveness, inherent safety, and eco‐friendliness. Here, a comprehensive overview on the basic mechanism of zinc–chalcogen batteries with their great advantages and intrinsic issues is provided. More detailed recent progress is summarized and the existing challenges with promising strategies are provided as well. First, four specific types of batteries are presented, including: zinc–sulfur, zinc–selenium, zinc–selenium sulfide, and zinc–tellurium batteries. Second, the remaining challenges within chalcogen‐based cathodes in the material preparation, physicochemical properties, and battery performance are summarized and discussed. Meanwhile, a series of constructive strategies are comprehensively put forward for optimizing electrochemical performance. Finally, the future research perspectives of zinc–chalcogen batteries are proposed for the exploration and innovation of next‐generation green zinc storage applications.

Minireview on Aqueous Zinc–Sulfur Batteries: Recent Advances and Future Perspectives

Minireview on Aqueous Zinc–Sulfur Batteries: Recent Advances and Future Perspectives

Fully integrated design of a stretchable kirigami-inspired micro-sized zinc–sulfur battery

This study presents the design and fabrication of the inaugural kirigami-inspired stretchable zinc–sulfur (Zn–S) battery with remarkable electro-chemo-mechanical properties.

Rational design of zinc powder anode with high utilization and long cycle life for advanced aqueous Zn-S batteries.

Aqueous zinc-sulfur (Zn-S) batteries are regarded as excellent candidates for energy storage applications due to their low cost, non-toxicity, and high theoretical energy density. However, the low utilization of the traditional thick foil-type Zn anode would severely restrict the overall energy density of Zn-S batteries. Herein, a mechanically and chemically stable powder-Zn/indium (pZn/In) anode with finite Zn loading was designed and constructed for enhancing the cycle stability of aqueous Zn-S batteries. Notably, the bifunctional In protective layer can inhibit the corrosion rate of highly active pZn and homogenize the Zn2+ flux during Zn plating/stripping. As a result, the obtained pZn/In anode exhibits a greatly improved cyclability of over 285 h even under a much harsh test condition (10 mA cm-2, 2.5 mA h cm-2, Zn utilization rate: ∼38.5%). Furthermore, when assembled with an S-based cathode at a negative/positive (N/P) capacity ratio ∼2, the full cell delivers a high initial specific capacity of ∼803 mA h g-1 and operates stably for over 300 cycles at 2C with a low capacity fading rate of ∼0.17% per cycle.

Recent advances in aqueous zinc–sulfur batteries: overcoming challenges for sustainable energy storage

This review outlines recent progress in aqueous zinc–sulfur batteries, highlighting electrolyte modification, additive engineering, and cathode enhancements. It also proposes future research directions to inspire solutions for overcoming challenges.

The influence of a new organic fertilizer based on sapropel on the results of germination of seeds of wheat, oats and mung bean

The article describes experience in studying the effect of a new complex biofertilizer based on natural raw materials - extracts of bird droppings and sapropel, namely: humic and fulvic substances from it, nitrogen-fixing microorganism Azotobacter chroococcum, fungus–ascomycete Trichoderma viride and a source of zinc sulfur - zinc sulfate. on germination and germination energy, seeds of winter wheat (Triticum aestivum) of Tanya variety, oats (Avena sativa L.) of Valdin 765 variety and legume mash (Vigna radiata) of Tajik 1 variety. The purpose of this study was to establish a sustainable positive effect by germinating seeds of winter wheat, oats and mung bean in Petri dishes when treated with a new complex biofertilizer based on sapropel and without treatment, to track the intensity of the germination energy of seeds of these plants on the third day and germination - on the seventh day. On the seventh day of germination of winter wheat in the experimental version, the length of seedlings exceeded the control version by 9.2%. In oats, the length of sprouts in the experimental version is 13.6% longer than in the control version.

Oxidative Degradation of Basic Red 29 by Persulfate Activated by Sulfur Composite Zinc

Herein, a composite zinc formed by ZnO and different zinc sulfur species is synthesized via a simple reduction of zinc sulfate by sodium sulfite under air. The obtained product is found to be very efficient in the activation of persulfate (PS) when compared to commercial ZnO. Diluted PS at 2 mM in homogeneous system allows the degradation of 24.83% of Basic Red 29 (BR29) after 120 min at 40 °C. The addition of 5 mg of the composite zinc increases the yield to 74.89%, while commercial ZnO registers 50.21% under the same conditions. The effectiveness of the composite sample is found to be due to the presence of ZnS and SO32− species that act as dopants for PS activation. The degradation reactions follow the pseudo‐first order with both catalysts. The main components involved in the degradation process are superoxide radical followed by singlet oxygen and then sulfate radical. Further application of ultrasounds at 40 kHz and addition of H2O2 at 1 mM reduces the reaction time for total degradation to 40 min with the composite zinc and 70 min with commercial ZnO.

Bifunctional electrolyte additive with redox mediation and capacity contribution for sulfur cathode in aqueous Zn-S batteries

Aqueous zinc-sulfur (Zn-S) battery has attracted much attention due to the ultrahigh theoretical capacity of S (1675 mA h g−1). Nevertheless, its lifespan is far from satisfactory owing to the sluggish reaction kinetics for ZnS conversion to S, and the formation of irreversible by-product of SO42− during charging. Herein, a novel bifunctional electrolyte additive thiourea (TU) was introduced to solve the above problems. It has been found that TU can undergo reversible redox reactions during cycles, which not only enhances the reversibility between ZnS and S but also contributes to extra capacities. Based on the ex-situ FTIR and XPS characterization, in combination with the electrochemical performance of thiourea and its derivatives, the influential mechanism of TU on the S@KB electrode was proposed. Its negative centers and positive centers of the intermediates can interact with ZnS to weaken the Zn-S bonds to improve the electrochemical dynamics. Simultaneously, the carbonium ions in the intermediate of TU show strong reactivity to ZnS so that the formation of SO42− can be inhibited. As a result, the S@KB electrode shows excellent cyclic performance with 763.7 mA h g−1 capacity after 300 cycles at 5 A/g, corresponding to a low decay rate of only 0.11 % per cycle. This work provides a promising electrolyte additive and an effective strategy to improve the reaction kinetics and cycle stability of Zn-S batteries.