Application Of Metal-air Batteries Research Articles

Orange peel derived activated carbon supported Ni–Co3O4 as an efficient electrocatalyst for oxygen evolution and reduction reaction in alkaline media

This study focuses on the development of a cost-effective electrocatalyst with excellent activity and stability for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), which is crucial for water electrolysis and fuel cell technologies. Waste orange peel is utilized as a carbon precursor to synthesize biomass-derived activated carbon (OPAC) with a unique three-dimensional sheet-like microstructure. Subsequently, a simple hydrothermal method is employed to modify the OPAC by introducing Ni-doped Co3O4, leading to the formation of a Ni–Co3O4/OPAC hybrid. We propose the Ni–Co3O4/OPAC hybrid as a highly efficient bifunctional electrocatalyst for both OER and ORR. Co3O4/OPAC and Co3O4 catalysts are also prepared for comparison. Remarkably, the Ni–Co3O4/OPAC hybrid exhibits significantly enhanced OER activity compared to Co3O4/OPAC and Co3O4 catalysts. It demonstrates a lower overpotential of 360 mV and a lower Tafel slope of 55.47 mV/dec, indicative of more efficient electrochemical performance. Moreover, in the ORR analysis, the Ni–Co3O4/OPAC hybrid displays a two-step pathway and achieves a higher ORR limiting current density compared to the Co3O4/OPAC and Co3O4 catalysts. These results highlight the synergistic effects of Ni and Co species, along with the unique properties of the OPAC support, which contribute to the enhanced activity, stability, and electron transfer characteristics of the Ni–Co3O4/OPAC hybrid. Furthermore, the improved electrical conductivity of the Ni–Co3O4/OPAC hybrid makes it a promising candidate for applications in metal-air batteries and other energy conversion devices. The utilization of waste orange peel as a carbon precursor and the facile synthesis method demonstrate the potential for cost-effective and sustainable electrocatalyst production. Overall, the Ni–Co3O4/OPAC hybrid represents a significant advancement in electrocatalyst design and holds promise for advancing the field of energy conversion and storage.

Breaking the Mutual-Constraint of Bifunctional Oxygen Electrocatalysis via Direct O─O Coupling on High-Valence Ir Single-Atom on MnOx.

Insufficient bifunctional activity of electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the major obstruction to the application of rechargeable metal-air batteries. The primary reason is the mutual constraint of ORR and OER mechanism, involving the same oxygen-containing intermediates and demonstrating the scaling limitations of the adsorption energies. Herein, it is reported a high-valence Ir single atom anchored on manganese oxide (IrSA-MnOx) bifunctional catalyst showing independent pathways for ORR and OER, i.e., associated 4e- pathway on high-valence Ir site for ORR and a novel chemical-activated concerted mechanism for OER, where a distinct spontaneous chemical activation process triggers direct O─O coupling. The IrSA-MnOx therefore delivers outstanding bifunctional activities with remarkably low potential difference (0.635V) between OER potential at 10mA cm-2 and ORR half-wave potential in alkaline solution. This work breaks the scaling limitations and provides a new avenue to design efficient and multifunctional electrocatalysts.

Electrohydrodynamic Printing Grid-Structured Catalytic Layers with Excellent Bending Resistance for Flexible Al-air Batteries.

The catalytic film of a flexible Al-air battery is generally a brittle film formed by brushing a slurry onto the surface of carbon cloth. Fatigue bending can easily lead to cracking of the catalytic film and shedding of the active material. This study innovatively proposes a novel grid-structured catalytic layer prepared by electrohydrodynamic printing. Experiments have verified that, compared with traditional catalytic films, the grid-structured catalytic layer exhibits excellent bending resistance. After 10 000 fatigue bending cycles, its relative resistance is ≈1/9 that of the traditional catalytic film. The printed grid-structured catalytic layer is applied to a flexible Al-air battery, which maintains a power density retention rate as high as 92% after the same number of bending cycles. Compared to traditional catalytic films, the electrodynamically printed grid-structured catalytic layer proposed in this study demonstrates both excellent electrochemical performance and bending resistance. This advancement holds significant importance for the development and application of flexible metal-air batteries.

Molten Salt-Assisted Synthesis of Ferric Oxide/M-N-C Nanosheet Electrocatalysts for Efficient Oxygen Reduction Reaction.

Efficient, stable, and low-cost oxygen reduction catalysts are the key to the large-scale application of metal-air batteries. Herein, high-dispersive Fe2O3 nanoparticles (NPs) with abundant oxygen vacancies uniformly are anchored on lignin-derived metal-nitrogen-carbon (M-N-C) hierarchical porous nanosheets as efficient oxygen reduction reaction (ORR) catalysts (Fe2O3/M-N-C, M═Cu, Mn, W, Mo) based on a general and economical KCl molten salt-assisted method. The combination of Fe with the highly electronegative O induces charge redistribution through the Fe-O-M structure, thereby reducing the adsorption energy of oxygen-containing substances. The coupling effect of Fe2O3 NPs with M-N-C expedites the catalytic activity toward ORR by promoting proton generation on Fe2O3 and transfer to M-N-C. Experimental and theoretical calculation further revealed the remarkable electronic structure evolution of the metal site during the ORR process, where the emission density and local magnetic moment of the metal atoms change continuously throughout their reaction. The unique layered porous structure and highly active M-N4 sites resulted in the excellent ORR activity of Fe2O3/Cu-N-C with the onset potential of 0.977V, which is superior to Pt/C. This study offers a feasible strategy for the preparation of non-noble metal catalysts and provides a new comprehension of the catalytic mechanism of M-N-C catalysts.

(Invited) Graphene-Supported Fe/Ni Single Atoms and Feni Alloy Nanoparticles as Bifunctional Oxygen Electrocatalysts for Rechargeable Zinc-Air Batteries

To alleviate the severe energy crisis and environmental problems caused by the massive and unsustainable consumption of fossil fuels, it is urgent to develop renewable energy conversion and energy storage technologies to reform the traditional energy structure. Batteries are considered as one of the most promising energy storage technologies due to their sustainability, high efficiency and less pollution. Among various battery storage devices, rechargeable zinc-air batteries (ZABs) have attracted widespread attention on account of their high theoretical energy density (1086 Wh kg– 1), low cost, abundant zinc resources, low operating temperature, and good stability and safety in aqueous environments. However, the kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurred on the air electrode during the discharging and charging processes are extremely sluggish, leading to low energy efficiency, which significantly limits the large-scale application of rechargeable ZABs. Pt-based electrocatalysts exhibit high ORR activities, while Ru- and Ir-based oxides are excellent OER electrocatalysts, but natural scarcity, high cost and poor durability seriously reduce the marketability and commercial competitiveness of rechargeable ZABs. Therefore, the development of robust, cost-effective and high-efficiency non-noble metal bifunctional ORR/OER electrocatalysts is of crucial significance for the practical application of rechargeable ZABs.As a promising alternative, earth-abundant transition metal (Fe, Co, Ni, etc.)-based materials have been extensively studied due to their relatively high electrocatalytic activity and durability. Thereinto, transition metal and nitrogen co-doped carbon (M-NC), especially Fe-NC, has been demonstrated to be the most effective ORR catalyst, and the active sites are generally considered as atomically dispersed metal coordinated to N atoms (M-Nx sites, x indicates the number of N atoms coordinating the metal). Nevertheless, M-NC catalysts only possess good ORR activity with poor OER performance. Bimetallic FeNi nanocomposites (metals, oxides, carbides, sulfides) are promising for OER. At high potentials, highly active FeNi oxyhydroxide species are generated on the surface of the FeNi-based electrocatalysts. Since ORR and OER depend on different catalytic active sites, an ideal bifunctional oxygen electrocatalysts should integrate M-NC complex with high ORR activity and bimetallic FeNi nanocomposite with a high OER activity to achieve bifunctionality. However, due to the intense competition between transition-metal single atoms and nanocomposites in the preparation process, it is challenging to combine them properly for superior bifunctional ORR/OER catalytic activity.Herein, we report a bifunctional oxygen electrocatalyst consisting of ZIF-derived carbon-anchored Fe/Ni single atoms and FeNi alloy nanoparticles; meanwhile, graphene is also introduced as carbon support to improve the uniformity of active sites (denoted as Fe/Ni-NC||FeNi@G). Benefiting from this unique composition and structure, Fe/Ni-NC||FeNi@G electrocatalyst displays excellent bifunctional ORR/OER activity and durability in rechargeable ZABs. This work provides an effective approach to designing highly efficient non-noble metal multifunctional catalysts for practical applications in rechargeable metal-air batteries. Acknowledgements Thanks for the financial support from the Shenzhen Science and Technology Innovation Committee (JCYJ20180507183818040).

PtCo nanoalloy embedded nitrogen-doped carbon nanotube for rechargeable Zn-air batteries

The large-scale application of metal-air batteries strongly depends on the development of cost-effective, highly efficient, and durable bifunctional oxygen catalysts. In this work, a facile approach for preparing the monodisperse PtCo nanoalloy anchored the nitrogen-doped carbon nanotubes (PtCo/NCNT) for zinc-air batteries is reported. The nitrogen-doped carbon shell prevents PtCo nanoalloy from exfoliation, dissolution, and aggregation and enables the accessibility of electrolytes to the alloy surface and the electron transfer. Besides, the strong interaction between PtCo nanoalloy and nitrogen-doped carbon can efficiently modulate the electronic structure of the formed active sites. When used as a cathode catalyst, the constructed rechargeable zinc-air battery presents higher power density (268 mW cm−2), specific capacity (840 mAh g−1), and excellent stability. More importantly, the PtCo/NCNT catalyst allows the all-solid-state cell to exhibit remarkable flexibility and high round-trip efficiency at various bending states, demonstrating a potential possibility to replace the conventional Pt/C and RuO2 catalysts.

Cu Regulating the Bifunctional Activity of Co-O Sites for the High-Performance Rechargeable Zinc-Air Battery.

The rational design of cost-effective and highly active electrocatalysts becomes the crucial energy storage technology to boost the kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), which hinders the large-scale application of metal-air batteries under the situation of increasingly pressing energy anxiety. Herein, the Co-based ZIF introduced the moderate amount of Cu2+-derived Cu/Co metal nanoparticles (NPs) embedded in carbon frameworks after high-temperature calcination. The Co-O bond on the surface of Co nanoparticles is modulated by adjacent Cu nanoparticles with the surface Cu-O bonds. The resulted increase of the Co2+/Co3+ ratio in 0.1CuCo-NC enhances the ORR/OER bifunctional catalytic kinetics along with the ΔE of 0.639 V. In situ Raman spectra of the catalyst on the three-electrode system as well as in the driven zinc-air battery (ZAB) show that the Co-O active sites regulated by Cu nanoparticles with Cu-O bonds maintain a periodic lattice expansion and compression during discharging and charging. The zinc-air battery based on 0.1CuCo-NC has a peak power density of up to 198.3 mW cm-2, a mass-specific capacity of 798.2 mAh g-1, and a cycling stability of 923 h at room temperature. This work makes up the research gap of a Co-based metal-organic framework (MOF)-derived catalyst regulated by a transition metal.

Structural insights, synthesis, and electrocatalysis of high entropy nanoparticles for fuel cell, metal-air battery, and water-splitting applications

High-entropy alloy nanoparticles (HEA-NPs) have recently sparked great interest in materials science. Their solid-solution states, derived from distinct HEA configurations, make them promising candidates for catalysts with exceptional activity, stability, and tunable performance. However, a comprehensive understanding of the underlying mechanisms governing their electrocatalytic behavior is still lacking, hindering the rational design of HEA electrocatalysts. This review summarizes the fundamental knowledge of HEA-NPs, including the structure-activity correlations of HEA-NPs, diverse synthesis strategies, and applications in electrochemical catalysis. The design strategies for guiding improvements in tunable performance were highlighted. The article concludes with insights, perspectives, and future directions, encapsulating the state-of-the-art knowledge and paving the way for further exploration in this dynamic field.

Boosting the ORR/OER Activity of Cobalt-Based Nano-Catalysts by Co 3d Orbital Regulation.

The transition metal oxides/sulfides are considered promising catalysts due to their abundant resources, facile synthesis, and reasonable electrocatalytic activity. Herein, a significantly improved intrinsic catalytic activity is achieved for constructing a Co-based nanocrystal (Co-S@NC) with the coordination of Co─S, Co─S─C, and Co─Nx─C. The calculational and experimental results demonstrate that the diversified chemical environment of Co-cations induces the transition of 3d orbitals to a high spin-state that exhibits the coexistence of Co2+ with fully occupied dπ orbitals and Co3+ with unpaired electrons in dπ orbitals. The diverse dπ orbitals occupation contributes to an elevated d-band center of Co ions, which accelerates oxygen reduction reaction and oxygen evolution reaction electrocatalytic kinetics of the Co-S@NC nanocrystal. Therefore, the Li-O2 batteries with Co-S@NC as cathode catalyst exhibit 300 cycles at the current density of 500 mA g-1 with a cut-off capacity of 1000 mAh g-1. Moreover, the ultrahigh discharge specific capacity of 34 587 mAh g-1 is obtained at a current density of 1000 mA g-1, corresponding to the energy density 949 Wh kg-1 of a prototype Li-O2 battery. The study on 3d orbital regulation of nanocrystals provides an innovative strategy for bifunctional electrocatalysts toward the practical application of metal-air batteries.

The Effect of Sulfur and Nitrogen Doping on the Oxygen Reduction Performance of Graphene/Iron Oxide Electrocatalysts Prepared by Using Microwave-Assisted Synthesis.

The synthesis of novel catalysts for the oxygen reduction reaction, by means of a fast one-pot microwave-assisted procedure, is reported herein and deeply explained. In particular, the important role of doping atoms, like sulfur and nitrogen, in Fe2O3-reduced graphene oxide nanocomposites is described to address the modification of catalytic performance. The presence of dopants is confirmed by X-ray Photoelectron Spectroscopy analysis, while the integration of iron oxide nanoparticles, by means of decoration of the graphene structure, is corroborated by electron microscopy, which also confirms that there is no damage to the graphene sheets induced by the synthesis procedure. The electrochemical characterizations put in evidence the synergistic catalysis effects of dopant atoms with Fe2O3 and, in particular, the importance of sulfur introduction into the graphene lattice. Catalytic performance of as-prepared materials toward oxygen reduction shows values close to the Pt/C reference material, commonly used for fuel cell and metal-air battery applications.

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 facile and green strategy for mass production of dispersive FeCo-rich phosphides@N,P-doped carbon electrocatalysts toward efficient and stable rechargeable Zn-air battery and water splitting

One key step for advancing the widespread practical application of rechargeable metal-air batteries and water electrolysis fundamentally relies on the development of cost-effective multifunctional electrocatalysts toward oxygen and hydrogen-involving reactions. The present work initiates a tofu-derived one-pot strategy for green, facile, and mass production of highly active and stable catalyst toward oxygen reduction/evolution and hydrogen evolution reactions, through the preparation of Fe/Co cross-linked tofu gel and the subsequent pyrolysis. Despite the free use of additional N/P precursors or pore-forming agents, the as-prepared materials comprise highly dispersive FeCo-rich phosphides nanoparticles and porous N,P co-doped carbon network inherited from the tofu skeleton. The resultant catalysts exhibit remarkably enhanced trifunctional activities as compared to the Fe2P and Co2P counterparts, along with better long-term stabilities than the benchmark RuO2 and Pt/C catalysts. Accordingly, the as-assembled Zn-air battery delivers a large power density (174 mW cm−2) with excellent cycle stability (the gap of charge/discharge voltage@10 mA cm−2 increases by 0.01 V after 720 h of operation, vs. 0.16 V of Pt/C-RuO2 based battery after 378 h). Furthermore, the as-constructed alkaline electrolyzer just requires a small voltage of 1.55 V@10 mA cm−2, which outperforms nearly all of those of biomass-derived electrocatalysts ever reported, and that of noble metal catalysts-based electrolyzers (1.72 V@10 mA cm−2 for Pt/C-RuO2), underscoring their bright future toward commercial applications in green energy conversion devices.

Amorphous Ni-Fe-Mo Oxides Coupled with Crystalline Metallic Domains for Enhanced Electrocatalytic Oxygen Evolution by Promoted Lattice-Oxygen Participation.

The crystalline/amorphous heterophase nanostructures are promising functional materials for biomedicals, catalysis, energy conversion, and storage. Despite great progress is achieved, facile synthesis of crystalline metal/amorphous multinary metal oxides nanohybrids remains challenging, and their electrocatalytic oxygen evolution reaction (OER) performance along with the catalytic mechanism are not systematically investigated. Herein, two kinds of ultrafine crystalline metal domains coupled with amorphous Ni-Fe-Mo oxides heterophase nanohybrids, including Ni/Ni0.5-a Fe0.5 Mo1.5 Ox and Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox , are fabricated through controllable reduction of amorphous Ni0.5 Fe0.5 Mo1.5 Ox precursors by simply tuning the amount of used reductant. Due to the suited component in metal domains, the special structure with dense crystalline/amorphous interfaces, and strong electronic coupling of their components, the resultant Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox nanohybrids show greatly enhanced OER activity with a low overpotential (278mV) to reach 10mAcm-2 current density and ultrahigh turnover frequency (38160h-1 ), outperforming Ni/Ni0.5-a Fe0.5 Mo1.5 Ox , Ni0.5 Fe0.5 Mo1.5 Ox precursors, commercial IrO2 , and most of recently reported OER catalysts. Also, such Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox nanohybrids manifest good catalytic stability. As revealed by a series of spectroscopy and electrochemical analyses, their OER mechanism follows the lattice-oxygen-mediated (LOM) pathway. This work may shed light on the design of advanced heterophase nanohybrids, and promote their applications in water splitting, metal-air batteries, or other clean energy fields.

Interfaces coupling of Co8FeS8-Fe5C2 with elevated d-band center for efficient water oxidation catalysis

Maximizing the oxygen evolution reaction (OER) catalytic activity of carbon coated core-shell electrocatalysts is significant for the application of water electrolyzers and rechargeable metal-air batteries, yet the modulation of the catalytic properties through interfaces coupling remains challenging. Here, we construct Fe5C2 phase interlayered between carbon shell and Co8FeS8 core (Co8FeS8-Fe5C2@C) for enhancing the alkaline OER catalytic performance. By altering the interlayer phase with Co1−xS as the control sample (Co8FeS8-Co1−xS@C), synchrotron X-ray absorption spectroscopy analysis integrated with density functional theory calculations indicate that the induced interfacial electron coupling of Co8FeS8-Co1−xS and Co8FeS8-Fe5C2 can upshift the d-band center toward Fermi level, optimalize Gibbs free energy for oxygen-containing intermediates, facilitate electron transfer between Co8FeS8 and carbon shell. Consequently, the target Co8FeS8-Fe5C2@C catalyst with stronger interface coupling and optimal electron modulation shows an significant overpotential (η10) decrease by 93 mV compared with Co8FeS8@C, along with a Tafel slop of 48.9 mV dec−1 and a long catalytic lifetime, outperforming commercial RuO2 and other reported analogous catalysts. This work opens up further opportunities of interlayer modification in carbon caoted core-shell catalyst to effictivly tailor the d-Band centers for effectively strengthen its catalytic performance.

Multimetallic Single-Atom Catalysts for Bifunctional Oxygen Electrocatalysis.

Multimetallic alloys have demonstrated promising performance for the application of metal-air batteries, while it remains a challenge to design multimetallic single-atom catalysts (MM-SACs). Herein, metal-C3N4 and nitrogen-doped carbon are employed as cornerstones to synthesize MM-SACs by a general two-step method, and the inherent features of atomic dispersion and the strong electronic reciprocity between the multimetallic sites have been verified. The trimetallic FeCoZn-SACs and quatermetallic FeCoCuZn-SACs are both found to deliver superior oxygen evolution reaction and oxygen reduction reaction activity, respectively, as well as outstanding bifunctional durability. Density functional theory calculations elucidate the crucial contribution of Co sites of FeCoCuZn-SACs to the efficient catalysis of both the ORR and the OER. More importantly, Zn-air batteries with FeCoCuZn-SACs as cathodic catalysts exhibit a high power density (252 mW cm-2), high specific capacity (817 mAh gZn-1), and considerable stability (over 225 h) for charging-discharging processes. This work provides a visual perspective for the advantages of MM-SACs toward oxygen electrocatalysis.

Microwave-assisted synthesis of N/S-doped CNC/SnO2 nanocomposite as a promising catalyst for oxygen reduction in alkaline media

In this study, we report an all-green approach for the synthesis of novel catalysts for oxygen reduction reaction (ORR) via a simple two-step procedure. In particular, conductive cellulose nanocrystals (CNCs) were obtained via pyrolysis, and a successive microwave-assisted hydrothermal process was employed to activate the carbon lattice by introducing sulfur (S) and nitrogen (N) dopants, and to decorate the surface with tin oxide (SnO2) nanocrystals.The successful synthesis of N/S-doped CNC/SnO2 nanocomposite was confirmed by X-ray Photoelectron Spectroscopy analysis, Energy Dispersive X-ray microanalysis, X-ray Diffraction and Field Emission Scanning Electron Microscopy. The synergistic effects of the dopants and SnO2 nanocrystals in modifying the catalytic performance were proved by various electrochemical characterizations. Particularly, the nanocomposite material reaches remarkable catalytic performance towards the ORR, close to the Pt/C benchmark, in alkaline environment, showing promising potential to be implemented in alkaline fuel cell and metal-air battery applications.

Lignin-derived sulfonate base metal-free N, S co-doped carbon microspheres doped with different nitrogen sources as catalysts for oxygen reduction reactions

The oxygen reduction reaction (ORR) is an important step in the widespread application of metal-air batteries, so it is necessary to study and develop low-cost and efficient metal-free carbon-based catalysts to catalyze the ORR reaction. Heteroatomic doping, especially N and S co-doped carbon materials, has received much focus as a promising ORR catalyst. Meanwhile, the lignin material has high carbon content, wide source, and low price, and has wide application prospects for the preparation of carbon material catalysts. Here we report a hydrothermal‑carbonation preparation method for the synthesis of carbon microspheres by utilizing lignin derivatives as carbon precursors. And a variety of N, S co-doped carbon microsphere materials were prepared by adding different nitrogen sources (urea, melamine, NH4Cl) to the microspheres. The N, S co-doped carbon microspheres (NSCMS-MLSN) catalysts achieved with NH4Cl as the nitrogen source displayed superior RR catalytic activity with high half-wave potential (E1/2 = 0.83 V vs. RHE) and current density (JL = 4.78 mA cm−2). This work provides some references on the method of preparing carbon materials co-doped with N and S and the choice of nitrogen sources.

Atomic Structure of Mn-Doped CoFe2O4 Nanoparticles for Metal–Air Battery Applications

We discuss the atomic structure of cobalt ferrite nanoparticles doped with Mn via an analysis based on combining atomic pair distribution functions with high energy X-ray diffraction and high-resolution transmission electron microscopy measurements. Cobalt ferrite nanoparticles are promising materials for metal–air battery applications. Cobalt ferrites, however, generally show poor electronic conductivity at ambient temperatures, which limits their bifunctional catalytic performance in oxygen electrocatalysis. Our study reveals how the introduction of Mn ions promotes the conductivity of the cobalt ferrite electrode.

NaCl-assisted synthesis of 2D hexagonal FeNC nanosheets as efficient oxygen reduction catalyst for metal-air batteries

Iron coordinated with nitrogen (FeNx) sites hosted in the micropores of carbon substrate offer excellent performance for the oxygen reduction reaction (ORR). Achieving a highly exposed and dispersed FeNx sites accessible for ORR is still challenging to date. In this work, two-dimensional hexagonal carbon nanosheets supported FeNx moieties (FeNC-NaCl-T) were synthesized via a molten NaCl-assisted pyrolysis strategy. Benefit from the high specific surface area (1371.635 m3·g−1) and highly dispersed FeNx sites, the optimized FeNC-NaCl-900 exhibits superior ORR activity with a high half-wave potential of 0.90 V in alkaline electrolyte. Impressively, with FeNC-NaCl-900 as the cathode catalyst in aqueous zinc–air battery, achieving a remarkable performance with a high peak power density of 177 mW·cm−2 and competitive durability (200 h). Furthermore, the Al-air battery equipped with FeNC-NaCl-900 attained an ultrahigh specific capacity of 2257.48 mAh·g−1 at a large discharge current of 100 mA cm−2. These findings provide guidance for the development of high performance FeNC catalysts and their applications in metal-air batteries.

Graphene-supported Fe/Ni single atoms and FeNi alloy nanoparticles as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

The development of inexpensive and high-performance bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of crucial significance for rechargeable metal-air batteries, but remains challenging. Herein, we report an ingenious bifunctional oxygen electrocatalyst integrating ZIF-derived carbon-anchored Fe/Ni single atoms, FeNi alloy nanoparticles, and graphene support (denoted as Fe/Ni-NC||FeNi@G). Synergizing highly active Fe single atoms for the ORR and highly efficient FeNi alloy nanoparticles for the OER, the as-constructed Fe/Ni-NC||FeNi@G catalyst exhibits outstanding bifunctionality; the potential gap between the OER potential at 10 mA cm–2 and the ORR half-wave potential is only 0.618 V, outperforming the benchmark Pt/C + Ir/C catalyst and most transition metal-based bifunctional catalysts reported in the literature. More importantly, the Fe/Ni-NC||FeNi@G-driven zinc-air battery (ZAB) delivers a maximum power density of ∼200 mW cm–2, a specific capacity of 876 mAh g–1, and excellent cycling stability with negligible voltage decay up to 500 hours (3000 cycles). This work provides an effective approach to designing highly efficient non-noble metal multifunctional catalysts for practical applications in rechargeable metal-air batteries.