Search

Rechargeable Zn–air batteries (ZABs) can play a significant role in the transition to a cleaner and more sustainable energy system due to their high theoretical energy density, high cell voltage, and environmental friendliness. ZAB's air cathode is the principal determinant in predicting the battery's overall performance, as it is responsible for catalyzing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during the discharging and charging process, respectively. In this work, a detailed optimization study of the architecture of the air cathode was carried out using the benchmark bifunctional oxygen electrocatalyst (Pt/C-RuO2). The air cathode composition and architecture were optimized regarding the choice of the commercial gas diffusion layer (GDL), the effect of hot pressing the catalyst layer (CL), and the optimum pore size of the current collector. The best cathode from this study shows a maximum power density (PDmax) of 167 mW/cm2, with a round trip efficiency and a voltage gap (Egap) of 59.8% and 0.78 V, respectively, indicating the air cathodes preparation approach proposed in this work as a promising strategy for the improvement of the overall performance of ZABs. [ABSTRACT FROM AUTHOR]

Developing efficient bifunctional electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is crucial for the large-scale application of rechargeable zinc–air batteries. Perovskite oxides are attractive candidates as bifunctional electrocatalysts. Herein, Ln0.5Sr0.5CoO3-δ (Ln = La, Pr and Sm) was prepared by the sol-gel method and evaluated as bifunctional electrocatalysts for both ORR and OER. Compare with La0.5Sr0.5CoO3-δ (LSC) and Sm0.5Sr0.5CoO3-δ (SSC), Pr0.5Sr0.5CoO3-δ (PSC) demonstrated the enhanced catalytic activity towards ORR with the limiting current density of 4.19 mA cm−2 at 0.40 V vs. RHE and OER with the potential of 1.75 V vs. RHE at 10 mA cm−2 as well as the Tafel slope of 105 mV dec−1. The higher Co3+/Co2+ ratio in PSC played an essential part in boosting the bifunctional electrocatalytic activities for ORR and OER. For demonstration, rechargeable zinc–air batteries with PSC as the air electrode displayed the maximum power density of 72 mW cm−2, the low charge-discharge voltage gap (1.01 V) at 10 mA cm−2 over 80 cycles and outstanding cycling stability. This work highlights the importance of A-site cations of the perovskite oxide as a valid strategy to improve ORR and OER activities. [ABSTRACT FROM AUTHOR]

Low-cost and highly efficient electrocatalysts for oxygen reactions are highly important for oxygen-related energy storage/conversion devices (e.g., solar fuels, fuel cells, and rechargeable metal-air batteries). In this work, a range of compositionally-tuned cerium-doped CoMn2O4 (Ce-CMO-X) spinels were prepared via oxidizing precipitation and subsequent crystallization method and evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The Ce modification into the CMO spinels lead to the changes of surface electronic structure. And Ce-CMO-X catalysts display better electrochemical performance than that of pristine CMO spinel. Among them, Ce-CMO-18% shows the best activity. The Ce-CMO-18% processes a higher ratio of Co3+/Co2+, Mn4+/Mn3+, which is beneficial to ORR performance, while the higher content of oxygen vacancies in Ce-CMO-18% make for better OER performance. Thus, the Ce-doped CMO spinels are potential candidates as bifunctional electrocatalysts for both ORR and OER in alkaline environments. Then, the hybrid Ce-CMO-18%/MWCNTs catalyst was also synthesized, which shows further enhanced ORR and OER activities. It displays an ORR onset potential of 0.93 V and potential of 0.84 V at density of 3 mA cm−2 (at 1600 rpm), which is comparable to commercial Pt/C. The OER onset potential and potential at a current density 10 mA cm-2 are 183 mV and 341 mV. The superior electrical conductivity and oxygen functional groups at the surface of MWCNTs can facilitate the interaction between metal oxides and carbon, which promoted the OER and ORR performances significantly. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in energy conversion and storage devices. Particularly, the bifunctional ORR/OER catalysts are core components in rechargeable metal–air batteries, which have shown great promise in achieving "carbon emissions peak and carbon neutrality" goals. However, the sluggish ORR and OER kinetics at the oxygen cathode significantly hinder the performance of metal–air batteries. Although noble metal-based catalysts have been widely employed in accelerating the kinetics and improving the bifunctionality, their scarcity and high cost have limited their deployment in the market. In this review, we will discuss the ORR and OER mechanisms, propose the principles for bifunctional electrocatalysts design, and present the recent progress of the state-of-the-art bifunctional catalysts, with the focus on non-noble metal-based materials to replace the noble metal catalysts in Zn–air batteries. The perspectives for the future R&D of bifunctional electrocatalysts will be provided toward high-performance Zn–air batteries at the end of this paper. [ABSTRACT FROM AUTHOR]

The development of high-performance non-noble metal-based oxygen electrocatalysts is crucial for the practical application of zinc–air batteries. Most of them suffer from low intrinsic activity and poor stability, failing to meet the needs of practical applications. Here, we report an efficient and durable bifunctional oxygen electrocatalyst of Fe@Fe-SAC composite (SAC stands for single atoms on carbon). A facile and ease-to-scale-up process synthesizes it. Fe single-atom and Fe nanoparticles are anchored on nitrogen-doped porous carbon, with the latter encapsulated by the graphitic shell. It exhibits appealing activity and durability in a basic electrolyte, requiring a half-wave potential of 0.805 V for oxygen reduction reaction (ORR) and an overpotential of only 348 mV to deliver a current density of 10 mA cm−2 for oxygen evolution reaction (OER). Both activities are comparable to the corresponding benchmarking electrocatalyst of Pt/C for ORR and IrO2 for OER. The superior activities are attributed to the strong electronic interaction between metal single-atom and nanoparticles. The favorable stability is ascribed to the physical encapsulation of carbon coatings on nanoparticles. This work presents a feasible scheme for designing and large-scale preparation of high-performance non-noble metal-based bifunctional oxygen electrocatalysts. [ABSTRACT FROM AUTHOR]

The smart choice of polyoxometalates (POMs) and the design of POM@carbon-based composites are promising tools for producing active electrocatalysts for both the oxygen reduction (ORR) and the oxygen evolution reactions (OER). Hence, herein, we report the preparation, characterization and application of three composites based on doped, multi-walled carbon nanotubes (MWCNT_N6) and three different POMs (Na12[(FeOH2)2Fe2(As2W15O56)2]·54H2O, Na12[(NiOH2)2Ni2(As2W15O56)2]·54H2O and Na14[(FeOH2)2Ni2(As2W15O56)2]·55H2O) as ORR and OER electrocatalysts in alkaline medium (pH = 13). Overall, the three POM@MWCNT_N6 composites showed good ORR performance with onset potentials between 0.80 and 0.81 V vs. RHE and diffusion-limiting current densities ranging from −3.19 to −3.66 mA cm−2. Fe4@MWCNT_N6 and Fe2Ni2@MWCNT_N6 also showed good stability after 12 h (84% and 80% of initial current). The number of electrons transferred per O2 molecule was close to three, suggesting a mixed regime. Moreover, the Fe2Ni2@MWCNT_N6 presented remarkable OER performance with an overpotential of 0.36 V vs. RHE (for j = 10 mA cm−2), a jmax close to 135 mA cm−2 and fast kinetics with a Tafel slope of 45 mV dec−1. More importantly, this electrocatalyst outperformed not only most POM@carbon-based composites reported so far but also the state-of-the-art RuO2 electrocatalyst. Thus, this work represents a step forward towards bifunctional electrocatalysts using less expensive materials. [ABSTRACT FROM AUTHOR]

Developing a highly stable and non-precious, low-cost, bifunctional electrocatalyst is essential for energy storage and energy conversion devices due to the increasing demand from the consumers. Therefore, the fabrication of a bifunctional electrocatalyst is an emerging focus for the promotion and dissemination of energy storage/conversion devices. Spinel and perovskite transition metal oxides have been widely explored as efficient bifunctional electrocatalysts to replace the noble metals in fuel cell and metal-air batteries. In this work, we developed a bifunctional catalyst for oxygen reduction and oxygen evolution reaction (ORR/OER) study using the mechanochemical route coupling of cobalt oxide nano/microspheres and carbon black particles incorporated lanthanum manganite perovskite (LaMnO3@C-Co3O4) composite. It was synthesized through a simple and less-time consuming solid-state ball-milling method. The synthesized LaMnO3@C-Co3O4 composite was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction spectroscopy, and micro-Raman spectroscopy techniques. The electrocatalysis results showed excellent electrochemical activity towards ORR/OER kinetics using LaMnO3@C-Co3O4 catalyst, as compared with Pt/C, bare LaMnO3@C, and LaMnO3@C-RuO2 catalysts. The observed results suggested that the newly developed LaMnO3@C-Co3O4 electrocatalyst can be used as a potential candidate for air-cathodes in fuel cell and metal-air batteries. [ABSTRACT FROM AUTHOR]

Rechargeable lithium–oxygen (Li-O2) batteries represent state-of-the-art electrochemical energy storage devices that provide high energy densities. However, their commercialization is challenging owing to their low charging/discharging efficiencies, short battery lives, high overpotentials, and high cathode manufacturing costs. In this study, we prepared a metal-free, N,P co-doped, porous activated carbon (N,P-PAC) electrode via KOH activation and P doping for application as a Li-O2 battery cathode. When used in a rechargeable Li-O2 battery, the N,P-PAC cathode showed a high specific discharge capacity (3724 mA h g−1 at 100 mA g−1), an excellent cycling stability (25 cycles with a limit capacity of 1000 mA h g−1), and a low charge/discharge voltage gap (1.22 V at 1000 mA h g−1). The N,P-PAC electrode showed a low overpotential (EOER-ORR) of 1.54 V. The excellent electrochemical performance of the N,P-PAC electrode can mainly be attributed to its large active area and oxygen-containing functional groups generated via KOH activation and P-doping processes. Therefore, the N,P-PAC prepared in this study was found to be a promising eco-friendly and sustainable metal-free cathode material for Li-O2 batteries. [ABSTRACT FROM AUTHOR]

Graphdiyne (GDY) is a two-dimensional (2D) electron-rich full-carbon planar material composed of sp2- and sp-hybridized carbon atoms, which features highly conjugated structures, uniformly distributed pores, tunable electronic characteristics and high specific surface areas. The synthesis strategy of GDY by facile coupling reactions under mild conditions provides more convenience for the functional modification of GDY and offers opportunities for realizing the special preparation of GDY according to the desired structure and unique properties. These structural characteristics and excellent physical and chemical properties of GDY have attracted increasing attention in the field of electrocatalysis. Herein, the research progress in the synthesis of atomic-level functionalized GDYs and their electrocatalytic applications are summarized. Special attention was paid to the research progress of metal-atom-anchored and nonmetallic-atom-doped GDYs for applications in the oxygen reduction reaction (ORR), the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) catalytic processes. In addition, several potential development prospects and challenges of these 2D highly conjugated electron-rich full-carbon materials in the field of electrocatalysis are presented. [ABSTRACT FROM AUTHOR]

An electrochemical nanoflowers manganese oxide (MnO2) catalyst has gained much interest due to its high stability and high specific surface area. However, there are a lack of insightful studies of electrocatalyst performance in nanoflower MnO2. This study assesses the electrocatalytic performances of nanoflower structure MnO2 for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in a zinc–air battery as a bifunctional electrocatalyst. The prepared catalyst was characterized in term of morphology, crystallinity, and total surface area. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the electrochemical behaviors of the as-prepared nanoflower-like MnO2. The discharge performance test for zinc–air battery with a MnO2 catalyst was also conducted. The results show that the MnO2 prepared at dwell times of 2, 4 and 6 h were nanoflowers, nanoflower mixed with nanowires, and nanowires with corresponding specific surface areas of 52.4, 34.9 and 32.4 g/cm2, respectively. The nanoflower-like MnO2 catalyst exhibits a better electrocatalytic performance towards both ORR and OER compared to the nanowires. The number of electrons transferred for the MnO2 with nanoflower, nanoflower mixed with nanowires, and nanowire structures is 3.68, 3.31 and 3.00, respectively. The as-prepared MnO2 nanoflower-like structure exhibits the best discharge performance of 31% higher than the nanowires and reaches up to 30% of the theoretical discharge capacity of the zinc–air battery. [ABSTRACT FROM AUTHOR]

Based on nanotechnology, nanocomposites are synthesized using nanoparticles (NP), which have some advantages in terms of multifunctional, economic, and environmental factors. In this review, we discuss the inorganic applications as well as catalytic applications of NPs. Recently, structural defects, heteroatomic doping, and heterostructures of such efficient ideal catalysts and their application as multifunctional catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. It has been verified that the catalysts used in oxygen reduction reaction and OER can be used effectively in metal/air batteries. Moreover, it has been reported that high-efficiency catalysts are required to implement urea oxidation reaction (UOR), which involves a six-electron reaction, as an electrochemical reaction. We expect that this review can be applied to sustainable and diverse electrochemistry fields. [ABSTRACT FROM AUTHOR]

This review summarizes recent progress in the development of cobalt-based catalytic centers as the most potentially useful alternatives to noble metal-based electrocatalysts (Pt-, Ir-, and Ru-based) towards the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in acid and alkaline media. A series of cobalt-based high-performance electrocatalysts have been designed and synthesized including cobalt oxides/chalcogenides, Co–Nx/C, Co-layered double hydroxides (LDH), and Co–metal-organic frameworks (MOFs). The strategies of controllable synthesis, the structural properties, ligand effect, defects, oxygen vacancies, and support materials are thoroughly discussed as a function of the electrocatalytic performance of cobalt-based electrocatalysts. Finally, prospects for the design of novel, efficient cobalt-based materials, for large-scale application and opportunities, are encouraged. [ABSTRACT FROM AUTHOR]

In this study, a low-cost and environmentally friendly method is developed to synthesize cobalt and nitrogen co-doped graphene-carbon nanotube aerogel (Co-N-GCA) as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The as-prepared Co-N-GCA has a hierarchical meso- and macroporous structure with a high N doping level (8.92 at. %) and a large specific surface area (456 m2 g−1). In an alkaline medium, the catalyst exhibits superior ORR electrocatalytic activity with an onset potential 15 mV more positive than Pt/C, and its diffusion-limiting current density is 29% higher than that of commercial Pt/C. The obtained Co-N-GCA is also highly active toward the OER, with a small overpotential of 408 mV at a current density of 10 mA cm−2. Its overall oxygen electrode activity parameter (ΔE) is 0.821 V, which is comparable to most of the best nonprecious-metal catalysts reported previously. Furthermore, Co-N-GCA demonstrates superior durability in both the ORR and the OER, making it a promising noble-metal-free bifunctional catalyst in practical applications for energy conversion and storage. [ABSTRACT FROM AUTHOR]

Scalable, low-cost and highly efficient catalysis of oxygen electrocatalytic reactions (ORR/OER) are required for the rapid development of clean and renewable energy conversion/storage technologies. Herein, two types of α-MnO2 nanorods were prepared under hydrothermal treatment at 150 °C for 0.5 h (MnO2-150-0.5) or 120 °C for 12 h (MnO2-120-12), then supported on N-doped ketjenblack carbon (N-KB) as bi-functional ORR/OER catalysts. Their electrocatalytic activities toward ORR and OER were investigated systematically. As a result, MnO2-150-0.5/N-KB displays superior ORR catalytic activity, with much more positive half-wave potential and much larger limiting current density (0.76 V and 6.0 mA cm−2), comparable to those of 20 wt. % Pt/C (0.82 V and 5.10 mA cm−2). MnO2-150-0.5/N-KB also shows high electron transfer number (3.86~3.97) and low yield of peroxides (1–7%) during ORR process in the whole potential range of 0–1.0 V (vs. RHE). Meanwhile, the MnO2-150-0.5/N-KB also exhibits better OER activity with low overpotential, comparable to IrO2/N-KB. The excellent electrocatalytic activity of MnO2-150-0.5/N-KB can be attributed to the synergistic effect, relatively smaller size, higher amount of Mn3+, and low charge transfer resistance. This work offers a new strategy for scalable preparation of more efficient and cost-effective α-MnO2 bi-functional oxygen catalysts. [ABSTRACT FROM AUTHOR]