Search Results (144)

Aqueous organic redox flow batteries (AORFBs) represent an advancing class of electrochemical energy storage systems showing considerable promise for large-scale grid integration due to their unique aqueous organic chemistry. However, the use of small-molecule active materials in AORFBs is significantly limited by the issue of stability and crossover. To address these challenges, we designed a high-water-solubility polymer cathode material, P-T-S, which features a polyvinylimidazole backbone functionalized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and sulfonate groups. P-T-S exhibits a solubility of 34 Ah L⁻¹ in water and 31 Ah L⁻¹ in 1.0 M NaCl aqueous solution (NaCl_aq). When paired with methyl viologen to assemble a pH-neutral AORFB with a theoretical capacity of 15 Ah L⁻¹, the system exhibits a material utilization rate of 92.0%, an average capacity retention rate of 99.74% per cycle (99.74% per hour), and an average Coulombic efficiency of 98.69% over 300 consecutive cycles at 30 mA cm⁻². This work provides a new design strategy for polymer materials for high-performance AORFBs. Full article

Lithium-ion batteries (LiBs) are utilized in numerous applications due to advancements in technology, and the recovery of end-of-life (EoL) LiBs is imperative for environmental and economic reasons. Pyrometallurgical and hydrometallurgical methods have been used in the recovery of metals such as Li, Co, and Ni in the EoL LiBs. Hydrometallurgical methods, which have been demonstrated to exhibit higher recovery efficiency and reduced energy consumption, have garnered increased attention in recent research. Inorganic acids, including HCl, HNO₃, and H₂SO₄, as well as organic acids such as acetic acid and citric acid, are employed in the hydrometallurgical recovery of these metals. It is imperative to acknowledge the environmental hazards posed by these acids. Consequently, solvometallurgical processes, which involve the use of organic solvents with minimal or no water, are gaining increasing attention as alternative or complementary techniques to conventional hydrometallurgical processes. In the context of solvent systems that have been examined for a range of solvometallurgical methods, deep eutectic solvents (DESs) have garnered particular interest due to their low toxicity, biodegradable nature, tunable properties, and efficient metal recovery potential. In this study, the leaching process of black mass containing graphite, LCO, NMC, and LMO was carried out in a short time using the ternary DES system. The ternary DES system consists of choline chloride (ChCl), glycolic acid (GLY), and ascorbic acid (AA). As a result of the leaching process of cathode powders in the black mass without any pre-enrichment process, Li, Co, Ni, and Mn elements passed into solution with an efficiency of over 95% at 60 °C and within 1 h. Moreover, the kinetics of the leaching process was investigated, and Density Functional Theory (DFT) calculations were used to explain the leaching mechanism. Full article

The conventional spent lithium-ion batteries (LIBs) recycling method suffers from complex processes and excessive chemical consumption. Hence, this study proposes an electrochemical strategy for achieving reductant-free leaching of high-valence transition metals and efficient separation of valuable components from spent cathode sheets (CSs). An innovatively designed sandwich-structured electrochemical reactor achieved efficient reductive dissolution of cathode materials (CMs) while maintaining the structural integrity of aluminum (Al) foils in a dilute sulfuric acid system. Optimized current enabled leaching efficiencies exceeding 93% for lithium (Li), cobalt (Co), manganese (Mn), and nickel (Ni), with 88% metallic Al foil recovery via cathodic protection. Multi-scale characterization systematically elucidated metal valence evolution and interfacial reaction mechanisms, validating the technology’s tripartite innovation: simultaneous high metal extraction efficiency, high value-added Al foil recovery, and organic removal through single-step electrochemical treatment. The process synergized the dissolution of CM particles and hydrogen bubble-induced physical liberation to achieve clean separation of polyvinylidene difluoride (PVDF) and carbon black (CB) layers from Al foil substrates. This method eliminates crushing pretreatment, high-temperature reduction, and any other reductant consumption, establishing an environmentally friendly and efficient method of comprehensive recycling of battery materials. Full article

Layered transition metal dichalcogenides (TMDs) have gained considerable attention as promising cathodes for aqueous zinc-ion batteries (AZIBs) because of their tunable interlayer architecture and rich active sites for Zn²⁺ storage. However, unmodified TMDs face significant challenges, including limited redox activity, sluggish kinetics, and insufficient structural stability during cycling. These limitations are primarily attributed to their narrow interlayer spacing, strong electrostatic interactions, the large ionic hydration radius, and their high binding energy of Zn²⁺ ions. To address these restrictions, an in situ organic polyaniline (PANI) intercalation strategy is proposed to construct molybdenum disulfide (MoS₂)-based cathodes with extended layer spacing, thereby improving the zinc storage capabilities. The intercalation of PANI effectively enhances interplanar spacing of MoS₂ from 0.63 nm to 0.98 nm, significantly facilitating rapid Zn²⁺ diffusion. Additionally, the π-conjugated electron structure introduced by PANI effectively shields the electrostatic interaction between Zn²⁺ ions and the MoS₂ host, thereby promoting Zn²⁺ diffusion kinetics. Furthermore, PANI also serves as a structural stabilizer, maintaining the integrity of the MoS₂ layers during Zn-ion insertion/extraction processes. Furthermore, the conductive conjugated PANI boosts the ionic and electronic conductivity of the electrodes. As expected, the PANI–MoS₂ electrodes exhibit exceptional electrochemical performance, delivering a high specific capacity of 150.1 mA h g⁻¹ at 0.1 A g⁻¹ and retaining 113.3 mA h g⁻¹ at 1 A g⁻¹, with high capacity retention of 81.2% after 500 cycles. Ex situ characterization techniques confirm the efficient and reversible intercalation/deintercalation of Zn²⁺ ions within the PANI–MoS₂ layers. This work supplies a rational interlayer engineering strategy to optimize the electrochemical performance of MoS₂-based electrodes. By addressing the structural and kinetic limitations of TMDs, this approach offers new insights into the development of high-performance AZIBs for energy storage applications. Full article

In this study, a Zn(CN)₂–V₂O₃–C composite cathode was synthesized via AC electrophoretic deposition (EPD) and evaluated for application in aqueous zinc-ion batteries (ZIBs). Here, we report for the first time a binder-free Zn(CN)₂–V₂O₃–C composite cathode, using AC-EPD to create an ultrathin architecture optimized for probing the electrode–electrolyte interface without interference from additives or bulk effects. The composite combines Zn(CN)₂ for structural support, V₂O₃ as the redox-active material, and carbon for improved conductivity. X-ray diffraction confirmed the presence of Zn(CN)₂ and V₂O₃ phases, while scanning electron microscopy revealed a uniform, ultrathin film morphology. Electrochemical analysis demonstrated a hybrid charge storage mechanism with a b-value of 0.64, indicating both capacitive and diffusion-controlled contributions. The electrode delivered a high specific capacity (~250 mAh/g at 500 mA/g) with stable cycling performance. These results highlight the potential of metal–organic framework-derived composites for high-performance ZIB cathodes. The composite is especially effective when prepared via AC-EPD, which yields ultrathin, uniform films with strong adhesion and low agglomeration. This enhances energy storage performance and provides a reliable platform for focusing on interfacial charge storage, excluding the effect of binders on electrochemical performance. Full article

Lithium–air batteries (LABs) possess the highest energy density among all energy storage systems, and have drawn widespread interest in academia and industry. However, many arduous challenges are still to be conquered, one of them is Li₂CO₃, which is a ubiquitous product in LABs. It is inevitably produced but difficult to decompose; therefore, Li₂CO₃ is perceived as the “Achilles’ heel of LABs”. Among various approaches to addressing the Li₂CO₃ issue, developing Li₂CO₃-decomposing redox mediators (RMs) is one of the most convenient and versatile, because they can be electrochemically oxidized at the gas cathode surface, then they diffuse to the solid-state products and chemically oxidize them, recovering the RMs to a pristine state and avoiding solid-state catalysts’ contact instability with Li₂CO₃. Furthermore, because of their function mechanism, they can double as catalysts for Li₂O₂/LiOH decomposition, which are needed in LABs/LOBs anyway regardless of Li₂CO₃ incorporation due to the sluggish kinetics of oxygen reduction/evolution reactions. This review summarizes the progress in Li₂CO₃-decomposing RMs, including halides, metal–chelate complexes, and metal-free organic compounds. The insights into and discrepancies in the mechanisms of Li₂CO₃ decomposition and corresponding catalysis processes are also discussed. Full article

Li/graphite fluoride (Li/CF_x) batteries display the highest energy densities among those of commercially available primary Li batteries but fail to satisfy the high-performance requirements of advanced applications. To address this drawback, two liquid organic dinitrates, namely, 1,4-butanediol dinitrate (BDE) and 2,2,3,3-tetrafluoro-1,4-butanediol dinitrate (TBD), were employed as high-energy energetic materials, and they were highly compatible with the electrolytes of Li/CF_x batteries. The use of Super P electrodes confirmed that the reduction reaction mechanisms of both nitrate ester-based compounds delivered considerable specific capacities, associated with discharge potentials matching that of the Li/CF_x battery. When considering the combined mass of the electrolyte and cathode as the active material, the overall energy densities of the Li/CF_x batteries increased by 25.3% (TBD) and 20.8% (BDE), reaching 1005.50 and 969.1 Wh/kg, respectively. The superior performance of TBD was due to the synergistic effects of the high electronegativities and levels of steric hindrance of the F atoms. Moreover, the nanocrystal LiF particles generated by TBD induced crack formation within the fluorinated graphite, increasing the lithium-ion accessible surface area and enhancing its utilization efficiency. These combined factors enhanced the reactivity of TBD and facilitated its involvement in electrochemical reactions, thus improving the capacity of the battery. The developed strategy enables the facile, cost-effective enhancement of the capacities of Li/CF_x batteries, paving the way for their practical use in energy-demanding devices. Full article

Developing efficient and durable non-precious metal catalysts for oxygen electrocatalysis in fuel cells and zinc–air batteries remains an urgent issue to be addressed. Herein, a bimetallic CoCe-NC catalyst is synthesized through pyrolysis of Co/Ce co-doped metal–organic frameworks (MOFs), retaining the inherently high surface area of MOFs to maximize the exposure of Co-N and Ce-N active sites. The electronic interaction between Co and Ce atoms effectively modulates the adsorption/desorption behavior of oxygen-containing intermediates, thereby enhancing intrinsic catalytic activity. In alkaline media, the CoCe-NC catalyst exhibits E_1/2 = 0.854 V electrocatalytic capability comparable to commercial Pt/C, along with superior methanol resistance and durability. Notably, CoCe-NC demonstrates an overpotential 84 mV lower than Pt/C at 300 mA cm⁻² in a GDE half-cell. When the catalyst is employed as a cathode in zinc–air batteries, it demonstrates an open-circuit voltage of 1.47 V, a peak power density of 202 mW cm⁻², and exceptional cycling durability. Full article

Lithium-ion batteries (LIBs) with high power, high capacity, and support for fast charging are increasingly favored by consumers. As a commercial electrode material for power batteries, LiFePO₄ was limited from further wide application due to its low conductivity and lithium-ion diffusion rate. The development of advanced architectures integrating rational conductive networks with optimized ion transport pathways represents a critical frontier in optimizing the performance of cathode materials. In this paper, a novel self-supporting cathode material (designated as LFP@LVP-CES) was synthesized through an integrated coaxial electrospinning and controlled pyrolysis strategy. This methodology directly converts LiFePO₄, Li₃V₂(PO₄)₃, and polyacrylonitrile (PAN)) into flexible, binder-free cathodes with a hierarchical structural organization. The 3D carbon nanofiber (CNF) matrix synergistically integrates LiFePO₄ (Li/Fe/PO_x) and Li₃V₂(PO₄)₃ (Li/V/PO_x) nanoparticles, where CNFs act as a conductive scaffold to enhance electron transport, while the PO_x polyanionic frameworks stabilize Li⁺ diffusion pathways. Morphological characterizations (SEM and TEM) revealed a 3D cross-connected carbon nanofiber matrix (diameter: 250 ± 50 nm) uniformly embedded with active material particles. Electrochemical evaluations demonstrated that the LFP@LVP-CES cathode delivers an initial specific capacity of 165 mAh·g⁻¹ at 0.1 C, maintaining 80 mAh·g⁻¹ at 5 C. Notably, the material exhibited exceptional rate capability and cycling stability, demonstrating a 96% capacity recovery after high-rate cycling upon returning to 0.1 C, along with 97% capacity retention over 200 cycles at 1 C. Detailed kinetic analysis through EIS revealed significantly reduced R_ct and increased Li⁺ diffusion. This superior electrochemical performance can be attributed to the synergistic effects between the 3D conductive network architecture and dual active materials. Compared with traditional coating processes and high-temperature calcination, the preparation of controllable electrospinning and low-temperature pyrolysis to some extent avoid the introduction of harmful substances and reduce raw material consumption and carbon emissions. This original integration strategy establishes a paradigm for designing freestanding electrode architectures through 3D structural design combined with a bimodal active material, providing critical insights for next-generation energy storage systems. Full article

Aqueous zinc-ion batteries (AZIBs) have attracted interest for their low cost and environmental friendliness. Two bipolar organic materials with different degrees of conjugation, pPMQT and pNTQT, were rationally designed and synthesized as cathode candidates for AZIBs based on 4,4′-diaminotriphenylamine (TPA), 2,7-diaminoanthraquinone (AQ), and two anhydrides. This molecular design features an increased conjugation and electron cloud density, thereby improving charge transport kinetics, specific capacity, and cycling stability. In comparison with pPMQ and pNTQ (n-type), pPMQT and pNTQT demonstrate better electrochemical characteristics. In this work, pNTQT shows outstanding performance. It exhibits an initial capacity of 349.79 mAh g⁻¹ at 0.1 A g⁻¹ and retains a specific capacity of 190.25 mAh g⁻¹ (87.6%) after 5000 cycles at 5 A g⁻¹. In comparison, pNTQ demonstrates a specific capacity of only 207.55 mAh g⁻¹ at 0.1 A g⁻¹, and after 5000 cycles at 5 A g⁻¹, its capacity retention rate is only 81.2%. At the same time, both pPMQT and pNTQT polymer films demonstrate attractive electrochromic (EC) properties, displaying reversible color transitions from yellow to dark blue in the UV–visible spectrum. This work lays the foundation for the further development of triphenylamine-based polyimide materials for application in AZIBs and electrochromism. Full article

Fabricating electrodes with high electrocatalytic efficiency is crucial for the commercial feasibility of vanadium redox flow batteries (VRFBs). In this study, metal–organic framework-derived ZnO and Fe₂O₃ with a high specific surface area were successfully synthesized via high-energy ball milling. The nanocomposite material (ZnO-Fe₂O₃) was prepared through ultrasonication and coated on the graphite felt using dip coating, serving as the positive electrode for the VRFB. These modified electrodes control polarization losses, leading to high voltage efficiency (VE) and energy efficiency (EE), even at high current densities. Consequently, the nanocomposite-modified electrode shows VE of 87% and EE of 84% at 50 mA/cm², surpassing the performance of individual materials. The nanocomposite material retains its EE without degradation over 250 cycles at a current density of 150 mA/cm². This enhanced performance is due to improved kinetics and reduced losses in the VO²⁺/VO₂⁺ redox couple, enabled by the nanocomposite material. Full article

In this study, we developed lithium–sulfur rechargeable batteries using chemically modified thermoplastic sulfur polymers as cathode active materials, aiming to effectively utilize surplus sulfur resources. The resulting high-sulfur-content resins exhibited self-healing properties, extensibility, and adhesiveness. By leveraging its high solubility in specific organic solvents, we successfully introduced sulfur-based compounds into porous carbon via vacuum impregnation using a solution, rather than conventional thermal impregnation. Charge–discharge measurements of lithium–sulfur (Li-S) secondary batteries assembled with this more uniform composite cathode, compared to those using elemental sulfur, demonstrated an increased discharge capacity in the initial cycles and at higher rates. Full article

The growing demand for efficient energy storage solutions has highlighted the potential of aqueous sodium-ion (Na⁺) batteries, known for their cost-effectiveness and environmental benefits. Despite their promise, challenges such as low specific capacities resulting from proton (H⁺) intercalation issues have limited their effectiveness. This study introduces a novel alkaline electrolyte environment using tetrabutylammonium hydroxide (TBAH) combined with chloride ions (Cl⁻) to improve the Na⁺ storage performance of manganese oxide (MnO₂) cathodes. The optimized electrolyte achieved a remarkable reversible capacity of 101 mAh g⁻¹ for γ-MnO₂ at a current density of 0.1 A g⁻¹, surpassing conventional aqueous solutions. The synergistic effect of TBAH and Cl⁻ not only suppresses H⁺ intercalation, but also prevents the formation of manganese hydroxide passivation layers during cycling. These advancements contribute to a better understanding of electrolyte design for high-performance Na⁺ storage electrodes, marking a significant step forward in aqueous sodium-ion battery technology. Full article

Lithium–sulfur batteries (LSBs) are considered candidates for next-generation energy storage systems due to their high theoretical energy density and low cost. However, their practical applications are constrained by the shuttle effect, lithium dendrites, low conductivity, and volume expansion of sulfur. Metal–organic frameworks (MOFs) have emerged as promising materials for addressing these challenges, owing to their exceptional adsorption and catalysis capabilities, coupled with a readily adjustable form-factor design. This review provides a broader perspective by comprehensively examining the applications of MOFs in LSBs, covering their roles in cathodes, separators, and electrolytes from multiple dimensions, including their reaction mechanisms, the development potential of MOFs as cathode materials, and the positive impacts on LSBs’ performance achieved through the preparation of MOFs and modifications of intermediate, separator, and electrolyte. Finally, we provide perspectives on future development directions in this field. Full article

Aqueous zinc batteries are emerging technologies for energy storage, owing to their high safety, high energy, and low cost. Among them, the development of low-cost and long-cycling cathode materials is of crucial importance. Currently, Zn-ion cathodes are heavily centered on metal-based inorganic materials and carbon-based organic materials; however, the metal–organic compounds remain largely overlooked. Herein, we report the electrochemical performance of metal phthalocyanines, a large group of underexplored compounds, as alternative cathode materials for aqueous zinc batteries. We discover that the selection of transition metal plays a vital role in affecting the electrochemical properties. Among them, iron phthalocyanine exhibits the most promising performance, with a reasonable capacity (~60 mAh g⁻¹), a feasible voltage (~1.1 V), and the longest cycling (550 cycles). The optimal performance partly results from the utilization of zinc chloride “water-in-salt” electrolyte, which effectively mitigates material dissolution and enhances battery performance. Consequently, iron phthalocyanine holds promise as an inexpensive and cycle-stable cathode for aqueous zinc batteries. Full article