Search Results (49)

The sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at air cathodes severely restrict the practical application of rechargeable zinc–air batteries (ZABs). Herein, equimolar lanthanide-doped spinel Co₃O₄ bifunctional electrocatalysts were synthesized via a citric acid-assisted sol–gel method. Among Ce-, Pr-, La-, and Sm-doped catalysts, Sm-Co₃O₄ exhibits the optimal electrocatalytic performance with a high ORR half-wave potential of 0.72 V and superior OER activity with an overpotential of 1.65 V at 10 mA cm⁻², achieving a minimal potential gap ΔE of 0.93 V. Rotating ring-disk electrode (RRDE) measurements and Koutecky–Levich (K–L) analyses confirm the exclusive 4e⁻ ORR pathway. Characterizations reveal that Sm doping modulates the electronic structure and lattice distortion of Co₃O₄, raises the Co²⁺/Co³⁺ ratio (0.59) and creates abundant oxygen vacancies, thereby significantly lowering the overpotentials for both ORR and OER. This study provides new insights for designing high-performance spinel-based bifunctional electrocatalysts for ZABs. Full article

Rechargeable zinc–air batteries (ZABs) are attractive energy storage systems owing to their high theoretical energy density, intrinsic safety, and low cost. Yet, their practical deployment is hindered by parasitic hydrogen evolution reaction (HER), zinc corrosion, and poor interfacial stability in alkaline electrolytes. Herein, biomass-derived carbon quantum dots (CQDs) synthesised from lemon peel waste via a hydrothermal route were employed as multifunctional electrolyte additives to regulate the zinc/electrolyte interface and mitigate these challenges. The CQDs exhibited oxygen-rich surface functionalities and quasi-spherical nanoscale morphology, enabling stable dispersion in 6 M KOH. Electrolyte modification with CQDs significantly altered the physicochemical properties of the electrolyte, increasing the zeta potential from −28.2 to +48.5 mV while maintaining high ionic conductivity. Electrochemical studies demonstrated progressive suppression of HER, evidenced by a shift in HER onset potential from 146 to 291 mV, an increase in overpotential at 10 mA cm⁻² from 398 to 477 mV, and an increase in Tafel slope from 82 to 130 mV dec⁻¹. Corrosion studies revealed enhanced zinc stability, with the charge transfer resistance increasing from 1.35 to 3.80 Ω and a maximum corrosion inhibition efficiency of 64.47% achieved at an optimal CQD loading of 1.0 mg. Furthermore, the CQD-modified electrolyte improved the average operating power density of the ZAB from approximately 4.5 to 5.5 mW cm⁻² and reduced charge–discharge polarisation during cycling. The enhanced performance is attributed to a combination of surface-controlled and transport-related processes, whereby oxygen-functionalized CQDs modify the electrical double layer, retard HER kinetics, and inhibit zinc corrosion. This work demonstrates a sustainable electrolyte engineering strategy for improving the durability and electrochemical performance of ZABs using biomass-derived carbon quantum dots. Full article

The development of highly efficient, stable, and cost-effective non-precious metal electrocatalysts to replace conventional platinum-based materials holds profound significance for accelerating the commercialization of advanced energy conversion devices, such as zinc–air batteries (ZABs). Herein, we propose a facile and highly efficient strategy to prepare a defect-rich, highly active nitrogen-doped porous carbon-based electrocatalyst (denoted U-Fe-N-C, urea-assisted iron–nitrogen–carbon material), via high-temperature co-pyrolysis of heme with urea. Our results demonstrate that urea not only serves as an excellent nitrogen source during pyrolysis, introducing abundant topological defects and heteroatom doping sites, but also induces the carbon substrate to form a hierarchical sponge-like porous structure with a high specific surface area. This unique microenvironment effectively prevents the agglomeration of iron species at high temperatures, achieving enhanced dispersion of iron species stabilized within the nitrogen-rich carbon matrix. Electrochemical evaluations reveal that under the optimal synthesis conditions (a precursor mass ratio of 1:3, calcination at 900 °C), U-Fe-N-C exhibits excellent oxygen reduction reaction (ORR) catalytic performance, delivering a half-wave potential of 0.731 V vs. RHE, and shows long-term operational durability that significantly surpasses that of commercial Pt/C. Furthermore, liquid rechargeable zinc–air batteries assembled with U-Fe-N-C as the air cathode deliver remarkable cycling stability, operating for up to 270 h of charge–discharge cycling without noticeable performance degradation. This study not only provides useful insights into the mechanisms of pore formation and assistance but also offers a practical perspective for the rational design and scalable synthesis of high-performance metal–nitrogen–carbon (M-N-C) electrocatalysts. Full article

Carbon-based bifunctional oxygen electrocatalysts with rationally designed architectures are essential for high-performance rechargeable zinc–air batteries (ZABs), yet the concurrent optimization of catalytic activity, durability, and mass transport remains challenging. Herein, hierarchical ZnCo carbon nanofibers/carbon nanotubes (CNFs@CNTs) are fabricated via single-nozzle electrospinning followed by melamine-assisted pyrolysis under a ZnCl₂-regulated atmosphere. During thermal treatment, Co species embedded within carbon nanofibers catalyze in situ carbon nanotube growth, while ZnCl₂ vapor modulates the carbonization process and surface chemistry, collectively generating a hierarchical CNFs@CNTs architecture with high surface area and abundant exposed active sites. As a result, ZnCo CNFs@CNTs exhibit outstanding bifunctional ORR/OER activity, surpassing Zn-free and Co-free counterparts. Combined structural and electrochemical analyses reveal that the synergistic interaction between Co active centers and Zn-assisted carbon structural regulation enhances reaction kinetics and long-term stability. When implemented as air electrodes in rechargeable ZABs, ZnCo CNFs@CNTs deliver high power density, reduced charge–discharge polarization, and excellent cycling durability, demonstrating strong practical applicability. This work presents an effective strategy for constructing hierarchical CNFs@CNTs composites via electrospinning and dual-component thermal regulation, offering new insights into the design of high-efficiency bifunctional air electrodes for advanced ZABs. Full article

Rechargeable zinc–air batteries (ZABs) are still impeded by the intrinsically sluggish kinetics of oxygen reduction and evolution reactions (ORR/OER) and by the instability or prohibitive price of state-of-the-art noble metal catalysts. Metal–organic frameworks (MOFs) have recently emerged as versatile sacrificial templates for next-generation air–cathode electrocatalysts. By programming pyrolytic or chemical conversion pathways, MOFs can be quantitatively transformed into hierarchically porous, heteroatom-doped carbon scaffolds that embed uniform metal, alloy, or metal-oxide nanodomains. The resulting architectures couple metallic conductivity with molecular-scale active site tunability, delivering exceptional ORR/OER activity, stability, and mass transport properties. This review critically examines the most recent advances in MOF-derived electrocatalysts for ZABs, establishing quantitative structure–composition–performance relationships across mono-, bi-, and multi-metallic systems. Emphasis is placed on deciphering how framework topology, metal–ligand coordination, and post-synthetic parameters dictate the density, electronic structure, and accessibility of surface-active moieties during catalyst evolution. We further dissect engineering strategies that enhance intrinsic activity via electronic modulation, bolster durability through encapsulation effects, and optimize hierarchical porosity for rapid O₂/water transport. This article concludes by outlining unresolved challenges and future research directions, including atomically precise active site construction, multi-scale compositional control, long-term reversibility under realistic ZABs cycles, scalable and green synthesis, providing a roadmap for translating MOF-derived catalysts from laboratory curiosities to commercially viable air–cathode materials. Full article

The rational design and synthesis of efficient and durable bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of great significance and challenging for rechargeable zinc–air batteries. While much attention has been devoted to enhancing ORR performance in recent studies, the effectiveness of OER is equally crucial for charging performance of Zn–air batteries. In this work, NH₂-MIL-101(Fe) is employed as a precursor to derive Fe-NC through a straightforward pyrolysis method. Subsequently, NiFe-LDH is synthesized on the surface of Fe-NC via a wet-chemical process to obtain Fe-NC@NiFe-LDH. Capitalizing on the synergistic interplay between Fe-NC, serving as the ORR active site, and NiFe-LDH, acting as the OER active site, Fe-NC@NiFe-LDH demonstrates remarkable bifunctional electrocatalytic performance, boasting a positive half-wave potential of 0.83 V for ORR and a low potential of 1.68 V for OER at a current density of 10 mA cm⁻², alongside exceptional stability in alkaline environments. Furthermore, the Fe-NC@NiFe-LDH-based Zn–air battery exhibits outstanding discharge and charge performance, maintaining excellent cycling stability over 600 h (3600 cycles). Full article

Rechargeable zinc–air batteries (ZABs) are promising candidates for sustainable energy storage owing to their high theoretical energy density, safety, and environmental compatibility. However, their practical application is hindered by sluggish oxygen evolution reaction (OER) kinetics and the high charging voltage required, which reduce energy efficiency and accelerate electrode degradation. Here, we report for the first time the beneficial role of potassium iodide (KI) as a reaction modifier in ZABs employing manganese dioxide (MnO₂) as a bifunctional catalyst. MnO₂ not only exhibits remarkable electrocatalytic activity toward the oxygen reduction reaction (ORR) but also catalyzes the iodide oxidation reaction (IOR), which proceeds at significantly lower potentials than the OER. As a result, KI-modified MnO₂ ZABs achieve a remarkably low charging voltage of ≈1.8 V and an energy efficiency of 69.9% at 5 mA/cm². Although the IOR is not fully reversible in alkaline media and its effectiveness depends on the iodide concentration in the electrolyte—which may decrease upon repeated discharge–charge cycling—the suppression of electrode degradation enables stable operation for more than 200 charge–discharge cycles. These findings demonstrate the synergistic effect of KI and MnO₂ in enabling an efficient ORR/IOR pathway, providing a sustainable and cost-effective alternative to noble metal catalysts and opening new perspectives for the practical development of high-performance ZABs. Full article

This work introduces a novel approach to enhancing the performance of zinc anodes in zinc–air batteries through a photopolymerizable organic–inorganic hybrid coating. Electrochemical tests were conducted in a neutral NaCl electrolyte, selected to minimize electrolyte carbonation, anode corrosion, and zinc dendrite formation. The behavior of bare and coated zinc electrodes was investigated using linear sweep voltammetry, electrochemical impedance spectroscopy (EIS), potentiostatic measurements, galvanostatic discharge tests, and charge-discharge tests, while morphological and structural characterizations were carried out by Atomic Force Microscopy (AFM), Raman spectroscopy, and X-ray Diffraction (XRD). The results confirmed that the hybrid coating acts as a corrosion-resistant barrier, enhancing the reversibility and stability of zinc electrodes through a barrier mechanism. Charge–discharge tests further confirmed the improved performance of the coated electrode, obtaining at a current density of 1 mA/cm², a coulombic efficiency of 92.61% and a capacity retention of 90.18%, respectively, after 16 cycles. These findings highlight the effectiveness of the photopolymerizable hybrid coating in improving the durability and rechargeability of zinc–air batteries. Full article

The commercialization of rechargeable alkaline zinc–air batteries has been constrained by critical challenges associated with the zinc electrode, including passivation, dendrite growth, and hydrogen evolution reaction. These issues severely limit the cycle life and pose a major barrier to large-scale industrial deployment. Integration of porous anode structures and electrode additives—two widely investigated approaches for mitigating challenges related to zinc anode—shows significant promise. However, effectively combining these approaches remains challenging. This study introduces a method for fabricating zinc anodes that can combine the benefits of a porous structure and electrode additive. The polytetrafluoroethylene (PTFE) polymer binder used in fabricating the anode material resulted in a stable scaffold, providing the desired anode porosity of approximately 60% and effectively anchoring ZnO nanoparticles. The zinc anodes prepared using a nickel mesh current collector without any electrode additives demonstrated stable cycling performance, sustaining 350 cycles at a current density of 60 mA g_Zn⁻¹ with a coulombic efficiency of approximately 95%. Incorporating 2 wt.% Bi₂O₃ as an electrode additive further enhanced the cycling performance, achieving 200 stable cycles with 100% coulombic efficiency under an increased current density of 120 mA g_Zn⁻¹, signifying the effectiveness of the proposed fabrication strategy. Full article

Developing cost-effective, sustainable, and high-performance air electrode catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a significant challenge in the advancement of rechargeable zinc–air batteries (ZABs). Herein, we successfully construct a vacancy-rich heterogeneous perovskite La_0.85Y_0.15Ni_0.7Fe_0.3O₃ (LYNF) hybridized with Co₃O₄ spinel nanoparticles using a simple chemical bath-assisted method. The Co₃O₄ composite LYNF material is systematically evaluated as the bifunctional catalyst for ZABs in the proportion of 25 wt%, 50w t%, and 75 wt% (denoted as LYNF-xCo₃O₄, x = 0.25, 0.5, 0.75). The results confirm an intimate coupling between the perovskite and spinel phases, along with a significant increase in oxygen vacancy concentration. Among the composites, LYNF-0.5Co₃O₄ exhibits the best performance, achieving an ORR onset potential of 0.813 V vs. RHE at −0.1 mA cm⁻² and a lower OER overpotential of 441 mV at 10 mA cm⁻². When applied as the air electrode catalyst in ZABs, LYNF-0.5Co₃O₄ displays the highest discharge voltage and a peak power density of 115 mW cm⁻², representing a 20% improvement over pristine LYNF. The enhanced performance of the LYNF-0.5Co₃O₄ composite is attributed to the accumulation of Co₃O₄ nanoparticles within the LYNF matrix, which introduces numerous electrochemically active sites and facilitates the charge and mass transport during the catalytic process in ZABs. Full article

Silicon carbide (SiC) and silicon nanoparticle-decorated carbon (Si/C) materials are electrodes that can potentially be used in various rechargeable batteries, owing to their inimitable merits, including non-flammability, stability, eco-friendly nature, low cost, outstanding theoretical capacity, and earth abundance. However, SiC has inferior electrical conductivity, volume expansion, a low Li⁺ diffusion rate during charge–discharge, and inevitable repeated formation of a solid–electrolyte interface layer, which hinders its commercial utilization. To address these issues, extensive research has focused on optimizing preparation methods, engineering morphology, doping, and creating composites with other additives (such as carbon materials, metal oxides, nitrides, chalcogenides, polymers, and alloys). Owing to the upsurge in this research arena, providing timely updates on the use of SiC and Si/C for batteries is of great importance. This review summarizes the controlled design of SiC-based and Si/C composites using various methods for rechargeable metal-ion batteries like lithium-ion (LIBs), sodium-ion (SIBs), zinc-air (ZnBs), and potassium-ion batteries (PIBs). The experimental and predicted theoretical performance of SiC composites that incorporate various carbon materials, nanocrystals, and non-metal dopants are summarized. In addition, a brief synopsis of the current challenges and prospects is provided to highlight potential research directions for SiC composites in batteries. Full article

The development of robust oxygen reduction reaction (ORR) catalyst with fast kinetics and good durability is significant for rechargeable zinc–air batteries (ZABs) but still remains a great challenge. Herein, inspired by the chain-like interconnective porous structure of plant luffa, an ORR catalyst of Co/CoCr₂O₄@ IPCF is fabricated, with Co and CoCr₂O₄ hybrid nanoparticles (NPs) embedding into interconnective porous carbon nanofibers (IPCF). Contributing to CoCr₂O₄ NPs stabilized Co active sites, the resulting ZABs assembled with Co/CoCr₂O₄@IPCF as an air cathode catalyst delivering sustainable cycling stability of 550 h, surpassing that of Co@IPCF based on ZABs (215 h). Also, the Co/CoCr₂O₄@IPCF has a high ORR performance with a half-wave potential (E_1/2) of 0.866 V in alkaline medium. The cycling stability originates from the IPCF carrier and the synergistic effect of Co NPs and CoCr₂O₄ NPs. The chain-like interconnective porous structure of the fibers provides more active sites and facilitates mass transfer to avoid the accumulation of OH⁻ and the exposure of H₂O₂, while the CoCr₂O₄ NPs can serve as a regulator for stabilizing the Co NPs electrochemical performance. Full article

Zinc–air batteries (ZABs) are crucial for renewable energy conversion and storage due to their cost-effectiveness, excellent safety, and superior cycling stability. However, developing efficient and affordable bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at the air cathode remains a significant challenge. Manganese (Mn)-based materials, known for their tunable oxidation states, adaptable crystal structures, and environmental friendliness, are regarded as the most promising candidates. This review systematically summarizes recent advances in Mn-based bifunctional catalysts, concentrating on four primary categories: Mn–N–C electrocatalysts, manganese oxides, manganates, and other Mn-based compounds. By examining the intrinsic merits and limitations of each category, we provide a comprehensive discussion of optimization strategies, which include morphological modulation, structural engineering, carbon hybridization, heterointerface construction, heteroatom doping, and defect engineering, aimed at enhancing catalytic performance. Additionally, we critically address existing challenges and propose future research directions for Mn-based materials in rechargeable ZABs, offering theoretical insights and design principles to advance the development of next-generation energy storage systems. Full article

Solid polymer electrolytes (SPEs) are gaining attention as viable alternatives to traditional aqueous electrolytes in zinc–air batteries (ZABs), owing to their enhanced performance and stability. In this study, anion-exchange solid polymer electrolytes (A-SPEs) were synthesized via electrophilic aromatic substitution and substitution reactions. Thin films were prepared using the solvent casting method and characterized using proton nuclear magnetic resonance (¹H-NMR), Fourier-transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The ion-exchange capacity (IEC), KOH uptake, ionic conductivity, and battery performance were also obtained by varying the degree of functionalization of the A-SPEs (30 and 120%, denoted as PSf30/PSf120, respectively). The IEC analysis revealed that PSf120 exhibited a higher quantity of functional groups, enhancing its hydroxide conductivity, which reached a value of 22.19 mS cm⁻¹. In addition, PSf120 demonstrated a higher power density (70 vs. 50 mW cm⁻²) and rechargeability than benchmarked Fumapem FAA-3-50 A-SPE. Postmortem analysis further confirmed the lower formation of ZnO for PSf120, indicating the improved stability and reduced passivation of the zinc electrode. Therefore, this type of A-SPE could improve the performance and rechargeability of all-solid-state ZABs. Full article

Developing efficient bifunctional oxygen reduction (ORR) and oxygen evolution (OER) electrocatalysts is critical for renewable energy technologies. Noble metal catalysts face limitations in cost, scarcity, and bifunctional compatibility. Herein, we report the synthesis of nickel nanoparticles encapsulated in nitrogen-doped carbon nanosheets (Ni@NC-T) via a solvothermal polymerization and pyrolysis process using a Ni-hexamine coordination framework (NiHMT) as a precursor. The Ni@NC-900 catalyst exhibits superior ORR and OER activity under alkaline conditions, with an ORR performance (half-wave potential = 0.86 V) comparable to commercial Pt/C and an OER overpotential of only 430 mV at 10 mA cm⁻². Structural analysis indicates that the hierarchical porous structure and high specific surface area (409 m² g⁻¹) of Ni@NC-900 facilitate the exposure of active sites and enhance mass transport. The surface-doped nitrogen species, predominantly in the form of pyridinic N and graphitic N, promote electron transfer during the ORR. Furthermore, its application as a bifunctional cathode in rechargeable zinc-air batteries results in a high power density of 137 mW cm⁻², surpassing the performance levels of many existing carbon-based bifunctional catalysts. This work highlights a facile strategy for the fabrication of transition metal-based catalysts encapsulated in MOF-derived carbon matrices, with promising potential for energy storage and conversion devices. Full article