Electrocatalysts For Rechargeable Zinc-air Batteries Research Articles

Pd-Co₃O₄/Acetylene Black Nanocomposite as an Efficient and Robust Bifunctional ORR/OER Electrocatalyst for Rechargeable Zinc-Air Batteries

Developing cost-effective and high-performing bifunctional electrocatalysts is pivotal for advancing rechargeable zinc-air batteries (ZABs). In this study, a Pd-Co₃O₄ loaded on acetylene black (Pd-Co₃O₄/C) electrocatalyst was developed with excellent properties for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) using reduced H₂PdCl₄ to modify Co₃O₄/C. The experimental findings indicate that the Pd-Co₃O₄/C electrocatalyst exhibits a favorable half-wave potential for ORR at 0.91 V, a feasible potential for OER at 1.48 V (measured at 10 mA/cm2), also minor Tafel slopes for both ORR (44.65 mV/dec) and OER (58.41 mV/dec). Additionally, it evidences a power density of 186 mW/cm2 in ZABs and good durability during galvanostatic charge-discharge cycling. The impressive performance of Pd-Co₃O₄/C can be ascribed primarily to the beneficial synergistic effect resulting from the composition of Co₃O₄ and Pd embedded within graphite carbon. This research lays the groundwork for the expansion of additional cost-effective and highly effective electrocatalysts in the coming years.

Fe3Co nanoparticles embedded carbon nanotube complex as effective bifunctional electrocatalysts for rechargeable zinc-air batteries

Fe3Co nanoparticles have been successfully embedded within ZIF-8 derived carbon nanotube complex using a simple solvent-heated self-assembly-pyrolysis strategy, it acts as an efficient ORR/OER bifunctional electrocatalyst and showed outstanding performance of excellent catalytic activity for ORR (E1/2 = 0.87 V at 0.1 M KOH) and OER (the overpotential at 10 mA cm−2 is 390 mV at 1 M KOH). Density functional theory (DFT) demonstrates that the introduction of iron and cobalt atoms significantly impacted on the adsorption energies of the reactive intermediates. In particular, the combination of cobalt and iron exhibited significantly enhanced ORR/OER activities, revealing an enhanced effect of synergistic interaction of FeCo site for bifunctional properties. It is used as Fe3Co1−NC in aqueous zinc-air battery (ZAB) and exhibited a high open-circuit voltage of 1.52 V, power density of 189.8 mW cm−2, and long cycle durability of 400 h. Flexible ZABs assembled exhibit high power density (81.59 mW cm−2) and long cycling durability (90 h).

Highly efficient bifunctional electrocatalyst for rechargeable zinc-air batteries: N, S dual-doped carbon encapsulating sulfur vacancy-rich FeCo/Fe-CoS nanoparticles

In this research, we present a highly efficient bifunctional electrocatalyst, N, S dual-doped carbon framework encapsulating sulfur vacancy-rich FeCo/Fe-CoS nanoparticles (VS-FeCo/Fe-CoS/NSC), synthesized via co-precipitation, sequential pyrolysis and sulfidation process. The prepared electrocatalyst exhibits exceptional performance in oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and rechargeable Zn-air batteries (ZABs). The VS-FeCo/Fe-CoS/NSC-based ZAB demonstrates outstanding bifunctionality, exhibiting high specific capacity of 793 mAh gZn−1 and peak power density of 164.68 mW cm−2. These values surpass those of noble metal-based ZAB, highlighting the superior electrochemical performance of the VS-FeCo/Fe-CoS/NSC catalyst. Such superior activity stems from synergistic effect of abundant heterointerfaces and sulfur vacancies in FeCo/Fe-CoS structure, resulting in enhanced charge transfer efficiency and reaction kinetic performance. Furthermore, the encapsulation of nanoparticles within the heteroatom-doped carbon matrix prevents aggregation and dissolution of active species, ensuring long-term stability during the battery operation. The electrochemical reversibility and stability of VS-FeCo/Fe-CoS/NSC are confirmed through extensive cycling tests, highlighting its potential for practical applications in energy conversion and storage systems.

Multilayer Porous Fe/Co-N-MWCNT Electrocatalyst For Rechargeable Zinc-Air Batteries.

The design of efficient, stable, low-cost non-precious metal-based electrocatalysts with enhanced oxygen reduction reaction (ORR) activity has garnered significant attention in the scientific community. This study introduces a novel electrocatalyst, Fe/Co-N-MWCNT, synthesized through the in-situ growth of ZIF-8 and Fe/Co-Phen on multi-walled carbon nanotubes (MWCNTs), followed by pyrolysis at varying temperatures to optimize its properties. The inclusion of Fe and Co during the pyrolysis process facilitated the creation of metal active sites and Fe-Co, enhancing electron transfer and ORR activity. Compared to Pt/C (E1/2=0.854 V, JL=4.90 mA cm-2), Fe/Co-N-MWCNT exhibited a similar half-wave potential (E1/2=0.812 V) and an improved limiting current density (JL=5.37 mA cm-2). Moreover, Fe/Co-N-MWCNT displayed remarkable stability, showing only a 7 mV negative shift in E1/2 after 2000 cycles. Ampere response testing indicated a current decay of only 7.8 % for Fe/Co-N-MWCNT after 10000 s, while Pt/C experienced a decay of about 18.4 %. The exceptional catalytic stability of Fe/Co-N-MWCNT positions it as a promising candidate for rechargeable zinc-air batteries, attributed to its high pyridinic nitrogen content, unique structure, and abundant metal active sites.

(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).

Designing Switchable Transition Metal Nitrides/Carbides from High-Entropy PBA Derivative As Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries

In response to the growing energy and environmental challenges, considerable endeavors have been directed towards the development of sustainable and eco-friendly energy technologies as alternatives to fossil fuels. Moreover, rechargeable zinc-air batteries (RZABs) stand out due to their high energy density and environmental friendliness, although the sluggish cathode oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics restrict RZABs performance. Prussian blue analogues (PBAs), owing to their highly porous structure and tunable morphology, are often utilized as the precursors of the materials. Particularly, high-entropy PBAs (HEPBAs), formed by blending five or more metals in a random lattice, have achieved enhanced thermal and chemical stability via a robust structure with multiple transition metal ions. Meanwhile, transition metal carbides (TMCs) were investigated for ZAB applications due to their higher catalytic activity. Herein, we introduced CNT into HEPBA nanoparticles, followed by calcination processes, resulting in the synthesis of high-entropy metal carbides on CNT (HE-TMCs/CNT) which are effective for the bifunctional OER and ORR performance. HE-TMCs/CNT demonstrate superior activity towards the ORR (E1/2 = 0.77 V) in a 0.1 M KOH solution and OER (η = 330 mV @10 mA cm−2) in a 1 M KOH solution. The ZAB with HE-TMCs/CNT as the cathode demonstrated an open-circuit voltage of 1.39 V, providing a high energy density of 71 mW cm-2 under a current density of 102 mA cm-2. It exhibited the ability to be charged and discharged in cycles for up to 40 hours, revealing good stability under an applied current density of 5 mA cm-2. These results offer a straightforward pathway for the development of efficient bifunctional electrocatalysts for high-performance RZABs. Figure 1

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.

Interfacial nanoparticles of Co2P/Co3Fe7 encapsulated in N-doped carbon nanotubes as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

Heterostructures have been generally proven beneficial to the electrocatalysis performance due to tailorable electronic structures. Herein, we develop a facile one-step strategy to synthesize Co2P/Co3Fe7 heterointerfacial nanoparticles encapsulated within N-doped carbon nanotubes (Co2P/Co3Fe7@N–C). The electrocatalyst exhibits a bifunctional oxygen evolution/reduction reaction (OER/ORR) activity (ΔE = 0.669 V) that far exceeds that of commercial Pt/C + Ir/C catalysts (ΔE = 0.76 V). In this study, Co2P/Co3Fe7@N–C-based zinc air batteries (ZABs) exhibit a higher power density (151.6 mW/cm2) and longer stability (1600 cycles) than commercial Pt/C + Ir/C-based ZABs (80 mW/cm2, 450 cycles). Density functional theory calculations reveal that the interfacial electronic interaction between Co2P and Co3Fe7 play key roles in boosting bifunctional ORR/OER efficiency. This work may open a new pathway for the rational design of superior bifunctional oxygen electrocatalysts for rechargeable metal-air batteries through interfacial engineering.

A novel layered cobalt oxide Ba2Co9O14 as an efficient and durable bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

In this work, a layered cobalt oxide Ba2Co9O14 (BCO), belongs to a Ban+1ConO3n+3(Co8O8) family composed by alternating CdI2 based layers (Co8O8) with n (111) perovskite blocks (Ban+1ConO3n+3), has been developed as a potential bifunctional oxygen electrocatalyst candidate for efficient and durable rechargeable zinc-air battery (ZAB) application. Because of the greatly increased the specific surface area caused by ball-milling, the as-milled BCO material exhibits strongly enhanced bifunctional electrocatalytic activity towards oxygen reduction and oxygen evolution reaction in alkaline medium. Moreover, the assembled BCO-based ZAB yields an effectively improved maximum output power density of 166 mW cm−2, a considerable specific capacity of 789 mAh g−1, and excellent charge-discharge cycle stability of over 250 h at 10 mA cm−2 with over 1500 cycles.

FeNi alloy embedded in three-dimensional nitrogen-doped porous carbon as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries

Iron‑nickel (FeNi) alloy is one of the efficient bifunctional oxygen electrocatalysts for zinc-air batteries (ZABs). However, FeNi alloy nanoparticles prepared by traditional synthesis strategies are easy to agglomerate and have non-uniform sizes, which is not conducive to the improvement of catalytic activity and stability. Here, we have successfully encapsulated two different kinds of nitrogen-rich metal phthalocyanines (MPcs) in situ doping in zeolitic imidazolate framework (ZIF-8) homogeneously by the “double solvents” method. The ligand nitrogen and macrocyclic structure of MPcs encapsulated in ZIF-8 not only helps metal dispersion and enhances the metal-ligand‑nitrogen (M-Nx) structure, but also enhances the graphitisation of three-dimensional (3D) porous carbon after pyrolysis. Thus, a FeNi alloy uniformly embedded in 3D nitrogen-doped porous carbon materials (FeNi@NC) was constructed in the subsequent pyrolysis process and used as an efficient bifunctional oxygen reduction/evolution (ORR/OER) electrocatalyst for rechargeable ZABs. Impressively, the FeNi@NC catalyst carries high half-wave potential (0.850 V) in ORR and the low overpotential (291 mV) in OER, significantly better than Pt/C (0.830 V) and RuO2 (307 mV), respectively. In addition, the rechargeable ZAB assembled with FeNi@NC air cathode has a specific capacity of 649 mW cm−2 and shows no significant degradation after 240 h of charging and discharging cycles. This study provides a new design idea for the manufacture of carbon-supported non-noble metal alloy catalysts with bifunctional oxygen catalytic activity, and verifies the feasibility of regulating the composition of non-noble metals to construct a rechargeable ZABs with excellent performance.

Surfactant-assisted synthesis of NiCo alloy with specific nanopore architecture as a bifunctional electrocatalyst for rechargeable zinc-air batteries

Designing the effective active sites and reaction areas of catalytic materials is important for the development of bifunctional electrocatalysts for zinc-air batteries (ZABs). In this paper, a catalyst with a uniform nanopore structure (noted as NiCo-PS) was one-pot synthesized by using transition metals nickel and cobalt as catalytic active components, sucrose as a carbon source, and triblock copolymers as a soft template. The N2 absorption and desorption isotherms curves show that the pore size distribution of NiCo-PS modified by surfactant is mainly in 3.6 nm range. NiCo-PS exhibits exceptional bifunctional electrocatalysis due to its effective triple-phase reaction interface from its mesoporous structure, with a positive half-wave potential of 0.758 V for ORR and a low overpotential of 390 mV at 10 mA ⋅ [Formula: see text] for OER. Furthermore, the rechargeable ZABs with the NiCo-PS catalyst exhibit a high open-circuit voltage of 1.31 V, a significant peak power density of 105 mA ⋅ [Formula: see text] at 0.56 V, and good stability throughout 270 h testing. This result offers valuable insights for designing catalysts that enhance the active region of the reaction within the cathodes of ZABs and hold significant promise for practical applications.

Multidimensional bimetallic-codoped MOF-derived M@N-CNTs bifunctional electrocatalysts for rechargeable zinc-air batteries

Multidimensional bimetallic-codoped MOF-derived M@N-CNTs bifunctional electrocatalysts for rechargeable zinc-air batteries

Highly Efficient Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries: Surface-Oxidized Cobaltous Fluoride Nanocrystals Embedded in Carbon Nanofibers

Highly Efficient Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries: Surface-Oxidized Cobaltous Fluoride Nanocrystals Embedded in Carbon Nanofibers

External Field-Responsive Ternary Non-Noble Metal Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

Despite the increasing effort in advancing oxygen electrocatalysts for zinc-air batteries (ZABs), the performance development gradually reaches a plateau via only ameliorating the electrocatalyst materials. Herein, a new class of external field-responsive electrocatalyst comprising Ni0.5Mn0.5Fe2O4 stably dispersed on N-doped Ketjenblack (Ni0.5Mn0.5Fe2O4/N-KB) is developed via polymer-assisted strategy for practical ZABs. Briefly, the activity indicator ΔE is significantly decreased to 0.618V upon photothermal assistance, far exceeding most reported electrocatalysts (generally >0.680V). As a result, the photothermal electrocatalyst possesses comprehensive merits of excellent power density (319mW cm-2), ultralong lifespan (5163 cycles at 25mA cm-2), and outstanding rate performance (100mA cm-2) for liquid ZABs, and superb temperature and deformation adaptability for flexible ZABs. Such improvement is attributed to the photothermal-heating-enabled synergy of promoted electrical conductivity, reactant-molecule motion, active area, and surface reconstruction, as revealed by operando Raman and simulation. The findings open vast possibilities toward more-energy-efficient energy applications.

CoFe formic-acid framework derived S, N co-doped carbon nanotube composites decorated with a bimetallic sulfide as a bifunctional electrocatalyst for rechargeable zinc–air batteries

A S, N co-doped carbon nanotube ORR/OER electrocatalyst loaded with a cobalt–iron alloy and Co8FeS8 nanoparticles was synthesized using a one-step pyrolysis method.

Hierarchical porous Fe/Ni-based bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

Developing sustainable and efficient bifunctional catalysts for oxygen reduction (ORR) and evolution (OER) reactions is challenging for energy conversion and storage. This work proposes a hierarchical carbon matrix decorated with nitrogen atoms (NC) as a support for obtaining high-performance electrocatalysts based on iron and nickel (Fe/Ni@N–C). The effect of different Fe:Ni ratios and the pyrolysis conditions on the catalyst performance were investigated by combining electrochemical tests, N2-adsorption-desorption, X-ray diffraction, Transmission Electron Microscopy, and X-ray photoelectron spectroscopy. Once optimized the pyrolysis conditions and the Fe:Ni ratio, the Fe/Ni@N–C catalyst showed high bifunctional OER/ORR activity in a three-electrode cell in an alkaline environment (KOH 1 M), with an overall ΔE for the ORR-OER reaction of 0.75 V. Fe/Ni@N–C was assembled in a rechargeable zinc-air battery, resulting in an excellent electrochemical performance in terms of power density (148.5 mWcm−2) and durability, outperforming the benchmark Pt/C–RuO2.

Facile hydrothermal synthesis of NiMoO4·xH2O nanorods-like structures as bifunctional oxygen electrocatalysts for rechargeable zinc-air batteries

Developing highly active and low-cost bifunctional catalyst materials to replace precious metal species is of utmost importance for the commercialization of clean and sustainable energy systems. In this report, homogenous NiMoO4·xH2O nanorods (NRs)-like structured materials were synthesized by an annealing-free hydrothermal method. The synthesized electrode electrochemical properties were determined by linear sweep voltammetry using a rotating ring disk electrode to determine the characteristics of oxygen reduction reaction in an O2-saturated electrolyte solution. For the oxygen evolution reaction, the NiMoO4·xH2O NRs electrocatalyst showed lower overpotential of 185 mV to obtain 10 mA cm−2. Furthermore, the NiMoO4·xH2O NRs electrocatalyst-based zinc (Zn)-air battery exhibited lower voltage gaps and smaller electrochemical impedance spectroscopy values than the Pt/C catalyst. Importantly, the NiMoO4·xH2O NRs-based battery (60 cycles (∼1100 min)) revealed excellent cycling stability results when compared with the Pt/C-based battery (30 cycles (∼550 min)). The NR structured electrode provided good steady potential after being subjected to a fixed current density of 10 mA cm−2 for 100 h. Therefore, these results demonstrate that the synthesized NiMoO4·xH2O NRs material is promising as a bifunctional electrocatalyst for rechargeable Zn-air batteries.

Nickel-iron layered double hydroxides interlinked by N-doped carbon network as bifunctional electrocatalysts for rechargeable zinc-air batteries

The rational design and fabrication of electrocatalysts with low cost and excellent bifunctional properties for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are desirable for high-efficiency rechargeable zinc-air batteries. Herein, we report the synthesis of NiFe LDHs nanoparticles interconnected by the one-dimensional N-doped carbon nanotubes (CNTs) and two-dimensional graphene nanosheets (NiFe-CNTs-rGO). The in-situ formed N-doped carbon and Fe-N-C active sites highly improve the ORR activity and the loading of NiFe LDHs nanoparticles promotes the OER. The integration of NiFe LDHs with intertwined CNTs and netlike rGO guarantees the good electrical conductivity of NiFe-CNTs-rGO. The unique composition and microstructure endow NiFe-CNTs-rGO with superior bifunctional activity toward ORR and OER. Moreover, the rechargeable zinc-air battery assembled with NiFe-CNTs-rGO electrocatalyst as air cathode shows a high capacity of 793 mA h g−1 and works stable for 100 h at 10 mA cm−2, outperforming commercial Pt/C and RuO2 mixture.

Accelerated deprotonation with a hydroxy-silicon alkali solid for rechargeable zinc-air batteries

Transition metal oxides are promising electrocatalysts for zinc-air batteries, yet surface reconstruction caused by the adsorbate evolution mechanism, which induces zinc-ion battery behavior in the oxygen evolution reaction, leads to poor cycling performance. In this study, we propose a lattice oxygen mechanism involving proton acceptors to overcome the poor performance of the battery in the OER process. We introduce a stable solid base, hydroxy BaCaSiO4, onto the surfaces of PrBa0.5Ca0.5Co2O5+δ perovskite nanofibers with a one-step exsolution strategy. The HO-Si sites on the hydroxy BaCaSiO4 significantly accelerate proton transfer from the OH* adsorbed on PrBa0.5Ca0.5Co2O5+δ during the OER process. As a proof of concept, a rechargeable zinc-air battery assembled with this composite electrocatalyst is stable in an alkaline environment for over 150 hours at 5 mA cm–2 during galvanostatic charge/discharge tests. Our findings open new avenues for designing efficient OER electrocatalysts for rechargeable zinc-air batteries.

In situ growth of surface-reconstructed aluminum fluoride nanoparticles on N, F codoped hierarchical porous carbon nanofibers as efficient ORR/OER bifunctional electrocatalysts for rechargeable zinc-air batteries

Modified porous carbon fibers have emerged as crucial electrocatalytic materials for zinc-air battery (ZAB) systems. However, most methods for preparing porous carbon fibers are complex and exhibit single functionality and poor catalytic activity, which hinders the development of ZABs. In this study, we design and synthesize a novel type of N, F codoped hierarchical porous carbon fiber with in situ growth of aluminum fluoride nanoparticles (AlF3@HPCNFs) through electrospinning and high-temperature carbonization. The N, F codoping effectively adjusts the charge density of neighboring carbon atoms and introduces additional active sites. Furthermore, the catalytic process induces surface reconstruction of AlF3 nanoparticles, allowing for their full exposure to the liquid electrolyte and accelerated catalytic reactions. Additionally, this interconnected hierarchical porous structure accelerates mass transfer at the oxygen/carbon-based substrate/electrolyte three-phase interfaces, thereby enhancing reaction kinetics and the accessibility of catalytic active sites, ultimately improving the utilization efficiency of these sites. Consequently, the AlF3@HPCNFs catalyst exhibits excellent bifunctional performance with a narrow potential difference (△E = 0.67 V). Moreover, the obtained bifunctional electrocatalyst is utilized for rechargeable ZABs, surpassing commercially available Pt/C + RuO2 cells in terms of high specific capacity (796 mAh gzn−1) and outstanding cycling stability (over 500 h). This research demonstrates the potential of AlF3@HPCNFs as a bifunctional electrocatalyst and introduces a simplified and effective method for the fabrication of metal fluoride-modified and hierarchically porous carbon nanofibers for rechargeable ZABs.