Performance Of Zinc-air Batteries Research Articles

Graphdiyne-Induced CoN/CoS2 Heterojunction: Boosting Efficiency for Bifunctional Oxygen Electrochemistry in Zinc-Air Batteries.

The performance of zinc-air battery is constrained by the sluggish rate of oxygen electrode reaction, particularly under high current discharge conditions where the kinetic process of the oxygen reduction reaction (ORR) decelerates significantly. To address this challenge, we present a novel phase transition strategy that facilitates the creation of a heteroatom-doped heterointerface (CoN/CoS2). The meticulously engineered CoN/CoS2/NC electrocatalyst displays a superior ORR half-wave potential of 0.87 V and an OER overpotential of 320 mV at 10 mA cm-2. Experimental and computational analysis confirm that the CoN/CoS2 heterostructure optimizes local charge distribution, accelerates electron transfer, and tunes active sites for enhanced catalysis. Notably, this heterojunction improves stability by resisting corrosion and degradation under harsh alkaline conditions, thus demonstrating superior performance and longevity in a custom-made liquid zinc-air battery. This research provides valuable practical and theoretical foundations for designing efficient heterointerfaces in electrocatalysis applications.

CuNi alloy anchored on dual-substrate TiOx/N-doped carbon nanofibers as a bifunctional electrocatalyst for rechargeable zinc-air batteries

Development of non-noble metal-based electrocatalysts to enhance the performance of zinc-air batteries (ZABs) is of great significance, but it remains a formidable challenge due to their poor stability and activity. Herein, a bifunctional CuNi-TiOx/NCNFS electrocatalyst, featuring with electron-rich copper-nickel (CuNi) alloy nanoparticles anchored on titanium oxide/N-doped carbon nanofibers (TiOx/NCNFS), is constructed by a dual-substrate loading strategy. The introduction of TiOx has led to a significant increase in the stability of the dual-substrate. The strong electronic interaction between CuNi and TiOx strengthens the anchoring of active metal sites, thus accelerating the electron transfer. Theoretical calculations unclose that NCNFS can regulate the charge distribution of TiOx, inducing the charge transfer from NCNFS → TiOx → CuNi, thereby reducing the d-band center of Cu and Ni, which is beneficial to the desorption of intermediate oxide species of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, CuNi-TiOx/NCNFS delivers a remarkable bifunctional performance with a low OER overpotential of 258 mV at 10 mA cm−2 and an ORR half-wave potential of 0.85 V. When assembled into ZABs, CuNi-TiOx/NCNFS shows a low potential gap of 0.64 V, a higher power density of 149.6 mW cm−2 at 330 mA cm−2, and an outstanding stability for 250 h at 5mA cm−2. This study provides a novel approach by constructing dual-substrate to tune the electronic structure of active metal sites for efficient rechargeable ZABs.

Improving the Oxygen Evolution Reaction Kinetics in Zn-Air Battery by Iodide Oxidation Reaction.

Zinc-air batteries (ZABs) have garnered considerable attention as a highly promising contender in the field of energy storage and conversion. Nevertheless, their performance is considerably impeded by the proliferation of dendrites on the Zinc anode and the slow kinetics of the redox reaction on the air cathode. Herein, taking Ag30%@LaCoO3 (Ag30%@LCO) heterojunction catalyst as the cathode, it is demonstrated that adding KI additives to the alkaline electrolyte can not only enhance the oxygen electrocatalytic reaction but also inhibit the formation of zinc anode dendrites, thereby achieving a comprehensive improvement in the performance of ZABs. Under the action of the KI additive, the optimized Ag30%@LCO catalyst shows a decreased overpotential from 460 to 220mV at j = 10mA cm-2, while the assembled ZAB shows reduced charging potential (1.8V), and long cycle stability (180h). Furthermore, the morphology characterization results indicate a reduction in dendrites on the Zn anode. Both experimental and calculated results indicate that the presence of I- as a reaction modifier alters the trajectory of the conventional oxygen evolution reaction, resulting in a more thermodynamically favorable pathway. The introduction of KI additives as electrolytes provides a straightforward approach to developing comprehensively improved ZABs.

Surface atomic bidirectional migration modulated electrocatalytic activity in Co2MnO4 nanoparticles

Polymetallic cationic spinel-type oxides are increasingly being used as catalysts for oxygen reduction/oxygen evolution reactions (ORR/OER). Here, we have modified the anti-spinel Co2MnO4 using a quenching strategy (CMO-Q) and demonstrated that the bidirectional migration of Co and Mn cations at the tetrahedral/octahedral positions is the essential reason for enhancing the ORR/OER performance. Electrochemical test results show that CMO-Q is better than Co2MnO4, OER initial potential decreased by 100 mV, and ORR current density increased from 4.2 to 7.3 mA cm−2 at 1600 rpm, with more stable CMO-Q-based zinc–air battery performance. Meanwhile, density functional theory calculations confirm that the primary factor contributing to the reduction of distance from the d-band center of Co and Mn to the Fermi level is the conductivity enhancement. This study offers insight into regulating the surface atomic migration and catalytic performance of spinel without compromising its stable structure.

M–Nx–C (M = Fe, Zn) bi-active sites booting oxygen reduction reaction and zinc-air battery performance

Fe/N/C is recognized promising catalyst for oxygen reduction reaction (ORR), playing a pivotal role in advancing the commercialization of proton exchange membrane fuel cells. However, an inadequate ORR activity hinders its potential applications. Here, we present the preparation of M–Nx–C (M = Fe, Zn) bi-active sites for promoting ORR. By the pyrolysis of benzimidazole salts, a porous coin-like iron-zinc-based nitrogen-doped carbon materials (FeZn-NC) catalyst was synthesized with abundant active sites. X-ray photoelectron spectroscopy and transmission electron microscopy characterizations indicated the successful doping of Zn and Fe within the carbon framework. Electrochemical measurements demonstrated great positive half-wave potential (0.90 V), high limiting current density (5.15 mA·cm−2), excellent methanol resistance, and good stability of FeZn-NC, compared to commercial Pt/C catalysts. Furthermore, an investigation into correlation between doping content of Fe and the ORR performance was carried out. As an cathode catalyst of zinc-air battery, FeZn-NC exhibited more significant advantages, including a high open-circuit voltage (1.54 V), enhanced power density (199.89 mW·cm−2), good specific capacity (771.9 mAh gZn−1), and enhanced stability compared to Pt/C. By presenting an approach for the controlled synthesis of metal-doped carbon materials, this work establishes the groundwork for potential applications in catalytic fields, as demonstrated by the prepared FeZn-NC.

Electron Spin Broken-Symmetry of Fe-Co Diatomic Pairs to Promote Kinetics of Bifunctional Oxygen Electrocatalysis for Zinc-Air Batteries.

Designing bifunctional catalysts to reduce the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) reaction barriers while accelerating the reaction kinetics is perceived to be a promising strategy to improve the performance of Zinc-air batteries. Unsymmetric configuration in single-atom catalysts has attracted attention due to its unique advantages in regulating electron orbitals. In this work, a seesaw effect in unsymmetric Fe-Co bimetallic monoatomic configurations is proposed, which can effectively improve the OER/ORR bifunctional activity of the catalyst. Compared with the symmetrical model of Fe-Co, a strong charge polarization between Co and Fe atoms in the unsymmetric model is detected, in whom the spin-down electrons around Co atoms are much higher than those spin-up electrons. The seesaw effect occurred between Co atoms and Fe atoms, resulting in a negative shift of the d-band center, which means that the adsorption of oxygen intermediates is weakened and more conducive to their dissociation. The optimized reaction kinetics of the catalyst leads to excellent performance in ZABs, with a peak power density of 215mW cm-2 and stable cycling for >1300 h and >4000 cycles. Flexible Zinc-air batteries have also gained excellent performance to demonstrate their potential in the field of flexible wearables.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm-2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance.

N-P covalent bond regulation of mesoporous carbon-based catalyst for lowered oxygen reduction overpotential and enhanced zinc-air battery performance

Developing sustainable metal-free carbon-based electrocatalysts is essential for the deployment of metal-air batteries such as zinc-air batteries (ZABs), among which doping of heteroatoms has attracted tremendous interest over the past decade. However, the effect of the heteroatom covalent bonds in carbon matrix on catalysis was neglected in most studies. Here, an efficient metal-free oxygen reduction reaction (ORR) catalyst is demonstrated by the N-P bonds anchored carbon (termed N,P-C-1000). The N,P-C-1000 catalyst exhibits superior specific surface area of 1362 m2 g−1 and ORR activity with a half-wave potential of 0.83 V, close to that of 20 wt% Pt/C. Theoretical computations reveal that the p-band center for C-2p orbit in N,P-C-1000 has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. The N,P-C-1000 assembled primary ZAB can attain a large peak power density of 121.9 mW cm−2 and a steady discharge platform of ∼1.20 V throughout 120 h. Besides, when served as the cathodic catalyst in a solid-state ZAB, the battery shows flexibility, conspicuous open circuit potential (1.423 V), and high peak power density (85.8 mW cm−2). Our findings offer a strategy to tune the intrinsic structure of carbon-based catalysts for improved electrocatalytic performance and shed light on future catalysts design for energy storage technologies beyond batteries.

Metal-Organic-Framework-Derived Nitrogen-Doped Carbon-Matrix-Encapsulating Co0.5Ni0.5 Alloy as a Bifunctional Oxygen Electrocatalyst for Zinc-Air Batteries.

The development of low-cost, high-performance oxygen electrocatalysts is of great significance for energy conversion and storage. As a potential substitute for precious metal electrocatalysts, the construction of efficient and cost-effective oxygen electrocatalysts is conducive to promoting the widespread application of zinc-air batteries. Herein, CoxNiyMOF nanoparticles encapsulated within a carbon matrix were synthesized and employed as cathode catalysts in zinc-air batteries. Co0.5Ni0.5MOF exhibits superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance and durability. The zinc-air battery assembled with Co0.5Ni0.5MOF as the air cathode exhibits a maximum power density of 138.6 mW·cm-2. These improvements are mainly attributed to the optimized metal composition of the cobalt-nickel alloy, which increases the specific surface area of the material and optimizes its pore structure. Significantly, the optimization of the electronic structure and active sites within the material has led to amplified ORR/OER activity and better zinc-air battery performance. This study underscores the immense promise of Co0.5Ni0.5MOF catalysts as feasible substitutes for commercial Pt/C catalysts in zinc-air batteries.

Heterostructure catalyst coupled wood-derived carbon and cobalt-iron alloy/oxide for reversible oxygen conversion

As promising energy-storage devices, zinc–air batteries (ZABs) exhibit slow reaction kinetics for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring at their electrodes. High-performance bifunctional catalysts must thus be synthesized to accelerate the reversible conversion of oxygen and improve the rate and overall performance of ZABs. Herein, we reported the promising prospects of self-supported composite electrodes composed of wood-derived carbon (WDC) and bimetallic cobalt-iron alloys/oxides (CoFe-CoFe2O4@WDC) as efficient electrocatalysts for alkaline ORR/OER. WDC provided a favorable three-phase interface for heterogeneous reactions owing to its layered porous structure and genetic stability, thereby enabling mass diffusion and improving reaction kinetics. The CoFe2O4 spinel surface was reduced to bimetallic CoFe alloy to form abundant heterostructure interfaces that promote electron transfer. Under alkaline conditions, the optimized composite electrode exhibited a remarkable high half-wave potential of 0.85 V and an exceptionally low overpotential of 1.49 V. It also exhibited stable performance over an impressive 2340 cycles in a ZAB. Theoretical calculations also confirmed that the heterointerface addresses the issue of proton scarcity throughout the reaction and actively facilitates the creation of O–O bonds during the reversible transformation of oxygen. This study introduces a new concept for developing bifunctional and efficient electrocatalysts based on charcoal and encourages the sustainable and high-value use of forest biomass resources.Graphical

Constructing Bipolar Dual-Active Sites through High-Entropy-Induced Electric Dipole Transition for Decoupling Oxygen Redox.

It remains a significant challenge to construct active sites to break the trade-off between oxidation and reduction processes occurring in battery cathodes with conversion mechanism, especially for the oxygen reduction and evolution reactions (ORR/OER) involved in the zinc-air batteries (ZABs). Here, using a high-entropy-driven electric dipole transition strategy to activate and stabilize the tetrahedral sites is proposed, while enhancing the activity of octahedral sites through orbital hybridization in a FeCoNiMnCrO spinel oxide, thus constructing bipolar dual-active sites with high-low valence states, which can effectively decouple ORR/OER. The FeCoNiMnCrO high-entropy spinel oxide with severe lattice distortion, exhibits a strong 1s→4s electric dipole transition and intense t2g(Co)/eg(Ni)-2p(OL) orbital hybridization that regulates the electronic descriptors, eg and t2g, which leads to the formation of low-valence Co tetrahedral sites (Coth) and high-valence Ni octahedral sites (Nioh), resulting in a higher half-wave potential of 0.87 V on Coth sites and a lower overpotential of 0.26 V at 10 mA cm-2 on Nioh sites as well as a superior performance of ZABs compared to low/mild entropy spinel oxides. Therefore, entropy engineering presents a distinctive approach for designing catalytic sites by inducing novel electromagnetic properties in materials across various electrocatalytic reactions, particularly for decoupling systems.

Electrochemically assisted polymerization synthesis of ZIF-derived Fe-N/C with high oxygen reduction reaction activity

Abstract The zeolitic imidazolate framework-8 (ZIF-8)-derived Fe-N/C catalysts show excellent oxygen reduction reactions (ORR) performance, but the harsh synthesis conditions and low yields have greatly limited their commercialization. Herein, we report an electrochemical-assisted polymerization method to produce a Fe-N/C structure (EC-Fe-N/C) with a high surface area (954.583 m2 g−1), high dispersion of Fe (2.2 wt %), and abundant N (2.05 wt %). The hierarchical structure exhibits excellent ORR activity (half-wave potential 0.88 V, in alkaline media) and outstanding zinc-air battery performance (energy density 821.3 mAh g−1 Zn, specific capacity 1017.1 Wh kg−1 Zn). This work may provide a simple and effective strategy to rationally design the Fe-N/C porous structure for highly efficient ORR activity.

Enhancing zinc–air battery performance by constructing three-dimensional N-doped carbon coating multiple valence Co and MnO heterostructures

Enhancing zinc–air battery performance by constructing three-dimensional N-doped carbon coating multiple valence Co and MnO heterostructures

Mitigating hydrogen evolution reaction and corrosion of zinc in electrically rechargeable zinc-air batteries using nanofluid electrolytes

Among various metal-air batteries, zinc-air batteries (ZABs) have received tremendous attention owing to their abundant resources, cost-free fuel from the atmosphere and ease of fabrication. The performance of ZABs depends on the bifunctional electrocatalyst deployed at the air-cathode and the hydrogen evolution reaction (HER) occurring at the anode. While the rate of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) improve the performance of ZAB, HER causes zinc corrosion and thereby affects the performance of ZAB. The corrosion of zinc is attributed to the fact that HER is thermodynamically favoured since the standard reduction potential of zinc is more negative than hydrogen. Herein, the onset and overpotential of HER are increased by the uniform dispersion of metal oxide nanoparticles in the native electrolyte (6 M KOH), thereby reducing zinc corrosion. Dispersion of 0.1 wt% of SiOx or ZnO nanoparticles increases the HER overpotential to 547 and 679 mV, respectively. The microscopic investigations confirm the inhibition of corrosion and dendritic growth of zinc. Besides these, nanofluid electrolytes enhance the kinetics of ORR and OER, thereby improving the performance of electrically rechargeable ZABs. Also, nanofluid electrolytes are stable over three months.

Spray Pyrolysis Regulated FeCo Alloy Anchoring on Nitrogen-Doped Carbon Hollow Spheres Boost the Performance of Zinc-Air Batteries.

Low-cost and high-efficiency non-precious metal-based oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalysts are the key to promoting the commercial application of metal-air batteries. Herein, a highly efficient catalyst of Fe0.18Co0.82 alloy anchoring on the nitrogen-doped porous carbon hollow sphere (FexCo1-x/N-C) is intelligently designed by spray pyrolysis (SP). The zinc in the SP-derived metal oxides and metal-organic framework volatilize at high temperature to construct a hierarchical porous structure with abundant defects and fully exposes the FeCo nanoparticles which uniformly anchor on the carbon substrate. In this structure, the coexistence of Fe0.18Co0.82 alloy and binary metal active sites (Fe-Nx/Co-Nx) guarantees the Fe0.2Co0.8/N-C catalyst exhibiting an excellent half-wave potential (E1/2 ═ 0.84V) superior to 20% Pt/C for ORR and a suppressed overpotential (280mV) than RuO2 for OER. Assembled rechargeable Zn-air battery (RZAB) demonstrates a promising specific capacity of 807.02mAhg-1, peak power density of 159.08mWcm-2 and durability without electrolyte circulation (550h). This work proposes the design concept of utilizing an oxide core to in situ consume the porous carbon shell for anchoring metal active sites and construct defects, which benefits from spray pyrolysis in achieving precise control of the alloy structure and mass preparation.

A superior zinc-air battery performance achieved by CoO/Fe3O4 heterostructured nanosheets.

CoO/Fe3O4 nanosheets exhibit a superior rechargeable zinc-air battery (ZAB) performance of 276 mW cm-2 and stability over 600 h. The all-solid-state ZAB also affords a high power density of 107 mW cm-2.

Non-noble metal single-atoms for oxygen electrocatalysis in rechargeable zinc-air batteries: recent developments and future perspectives.

Ever-growing demands for zinc-air batteries (ZABs) call for the development of advanced electrocatalysts. Single-atom catalysts (SACs), particularly those for isolating non-noble metals (NBMs), are attracting great interest due to their merits of low cost, high atom utilization efficiency, structural tunability, and extraordinary activity. Rational design of advanced NBM SACs relies heavily on an in-depth understanding of reaction mechanisms. To gain a better understanding of the reaction mechanisms of oxygen electrocatalysis in ZABs and guide the design and optimization of more efficient NBM SACs, we herein organize a comprehensive review by summarizing the fundamental concepts in the field of ZABs and the recent advances in the reported NBM SACs. Moreover, the selection of NBM elements and supports of SACs and some effective strategies for enhancing the electrochemical performance of ZABs are illustrated in detail. Finally, the challenges and future direction in this field of ZABs are also discussed.

Atomically dispersed multi-site catalysts: bifunctional oxygen electrocatalysts boost flexible zinc–air battery performance

Based on the advancements in atomically dispersed multi-site catalysts for FZABs, this review discusses the design methodologies to regulate the performance of bifunctional oxygen electrocatalysts from the electronic and geometric structures.

Maximizing active site utilization in carbocatalysts for high-performance oxygen reduction reactions and zinc–air battery-powered capacitive deionization

A structure-property relationship is disclosed between electrochemical surface area and active site utilization in ORR. The optimized NPC–Zn exhibits excellent zinc–air battery performance, serving as a power to drive capacitive deionization devices.

Robust bifunctionality in an oxygen electrode via core-shell heterostructure construction.

A Co-CoSe core-shell heterostructure encapsulated into nitrogen-doped carbon nanotubes enables superior zinc air battery performance (172 mW cm-2) and stability (970 h). The enhanced bifunctionality and stability originates from the modulated d band center and confinement effect, respectively.