A Superior Bifunctional Electrocatalyst in Which Directional Electron Transfer Occurs Between a Co/Ni Alloy and Fe─N─C Support.

Stable, efficient, and economical bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are needed for rechargeable Zn-air batteries. In this study, a directional electron transfer pathway is exploited in a spatial heterojunction of CoyNix@Fe─N─C heterogeneous catalyst for effective bifunctional electrolysis (OER/ORR). Thereinto, the Co/Ni alloy is strongly coupled to the Fe─N─C support through Co/Ni─N bonds. DFT calculations and experimental findings confirm that Co/Ni─N bonds play a bridging role in the directional electron transfer from Co/Ni alloy to the Fe─N─C support, increasing the content of pyridinic nitrogen in the ORR-active support. In addition, the discovered directional electron transfer mechanism enhances both the ORR/OER activity and the durability of the catalyst. The Co0.66Ni0.34@Fe─N─C with the optimal Ni/Co ratio exhibits satisfying bifunctional electrocatalytic performance, requiring an ORR half-wave potential of 0.90 V and an OER overpotential of 317 mV at 10 mA cm-2 in alkaline electrolytes. The assembled rechargeable zinc-air batteries (ZABs) incorporating Co0.66Ni0.34@Fe─N─C cathode exhibits a charge-discharge voltage gap comparable to the Pt/C||IrO2 assembly and high robustness for over 60 h at 20 mA cm-2.

Plasma-Engineering of Oxygen Vacancies on NiCo2O4 Nanowires with Enhanced Bifunctional Electrocatalytic Performance for Rechargeable Zinc-air Battery.

Designing an efficient, durable, and inexpensive bifunctional electrocatalyst toward oxygen evolution reactions (OER) and oxygen reduction reactions (ORR) remains a significant challenge for the development of rechargeable zinc-air batteries (ZABs). The generation of oxygen vacancies plays a vital role in modifying the surface properties of transition-metal-oxides (TMOs) and thus optimizing their electrocatalytic performances. Herein, a H2/Ar plasma is employed to generate abundant oxygen vacancies at the surfaces of NiCo2O4 nanowires. Compared with the Ar plasma, the H2/Ar plasma generated more oxygen vacancies at the catalyst surface owing to the synergic effect of the Ar-related ions and H-radicals in the plasma. As a result, the NiCo2O4 catalyst treated for 7.5 min in H2/Ar plasma exhibited the best bifunctional electrocatalytic activities and its gap potential between Ej = 10 for OER and E1/2 for ORR is even smaller than that of the noble-metal-based catalyst. In situ electrochemical experiments are also conducted to reveal the proposed mechanisms for the enhanced electrocatalytic performance. The rechargeable ZABs, when equipped with cathodes utilizing the aforementioned catalyst, achieved an outstanding charge-discharge gap, as well as superior cycling stability, outperforming batteries employing noble-metal catalyst counterparts.

Aluminium, Nitrogen-Dual-Doped Reduced Graphene Oxide Co-Existing with Cobalt-Encapsulated Graphitic Carbon Nanotube as an Activity Modulated Electrocatalyst for Oxygen Electrocatalyst for Oxygen Electrochemistry Applications.

There is a rising need to create high-performing, affordable electrocatalysts in the new field of oxygen electrochemistry. Here, a cost-effective, activity-modulated electrocatalyst with the capacity to trigger both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in an alkaline environment is presented. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with cobalt-encapsulated carbon nanotube units. Based on X-ray Absorption Spectroscopy (XAS) studies, it is established that the superior reaction kinetics in Al, Co/N-rGCNT over their bulk counterparts can be attributed to their electronic regulation. The Al, Co/N-rGCNT performs as a versatile bifunctional electrocatalyst for zinc-air battery (ZAB), delivering an open circuit potential ≈1.35 V and peak power density of 106.3 mW cm-2, which are comparable to the system based on Pt/C. The Al, Co/N-rGCNT-based system showed a specific capacity of 737 mAh gZn -1 compared to 696 mAh gZn -1 delivered by the system based on Pt/C. The DFT calculations indicate that the adsorption of Co in the presence of Al doping in NGr improves the electronic properties favoring ORR. Thus, the Al, Co/N-rGCNT-based rechargeable ZAB (RZAB) emerges as a highly viable and affordable option for the development of RZAB for practical applications.

Decoding the Mechanisms of Reversibility Loss in Rechargeable Zinc-Air Batteries.

Attaining high reversibility of the electrodes and electrolyte is essential for the longevity of secondary batteries. Rechargeable zinc-air batteries (RZABs), however, encounter drastic irreversible changes in the zinc anodes and air cathodes during cycling. To uncover the mechanisms of reversibility loss in RZABs, we investigate the evolution of the zinc anode, alkaline electrolyte, and air electrode through experiments and first-principles calculations. Morphology diagrams of zinc anodes under versatile operating conditions reveal that the nanosized mossy zinc dominates the later cycling stage. Such anodic change is induced by the increased zincate concentration due to hydrogen evolution, which is catalyzed by the mossy structure and results in oxide passivation on electrodes and eventually leads to low true Coulombic efficiencies and short life spans of batteries. Inspired by these findings, we finally present a novel overcharge-cycling protocol to compensate for the Coulombic efficiency loss caused by hydrogen evolution and significantly extend the battery life.

Simply prepared electrocatalyst of CoFe alloy and nitrogen-doped carbon with multi-dimensional structure and high performance for rechargeable zinc-air battery.

Simple and green preparation of highly-performed electrocatalysts for reaction both at cathode (oxygen reduction reaction (ORR)) and anode (oxygen evolution reaction (OER)) is crucial for boosting the application of meta-air battery. CoFe alloy and nitrogen doped carbon (CoFe-NC) material was prepared by a one-step carbonization procedure to construct a highly efficient electrocatalysis in this work. CoFe-NC displays a three-dimensional (3D) flower-like morphology composed of ordered stacked 2D nanosheets, which is entangled by 1D carbon nanotubes (CNTs). Its structure and electrocatalytic performance are compared with that of nitrogen doped carbon materials obtained from 2D zeolitic-imidazolate frameworks (ZIF) with no metal or single metal, as well as 3D ZIF with bimetal. Benefiting from the multi-dimensional structure of bimetal nanoparticles, 1D CNTs, 2D nanosheets, and 3D flowers, as well as the abundant active sites of Co/Fe-Nxand pyridine nitrogen, CoFe-NC displays a high half-wave potential of 0.896 V for ORR and low overpotential of 370 mV at 10 mA cm-2for OER. Furthermore, compared with the primary and rechargeable Zn-air batteries fabricated with commercial Pt/C-RuO2catalysts, the CoFe-NC catalysts assembled Zn-air batteries show a higher specific capacity (812.2 mAh g-1), open circuit potential (1.59 V), power density (183.4 mW cm-2), and stability. Hence, a facile and environmental-friendly strategy is provided for rational design and synthesis of bifunctional electrocatalysts for zinc-air batteries.

Amorphous Iron(III)-Borate Nanolattices as Multifunctional Electrodes for Self-Driven Overall Water Splitting and Rechargeable Zinc-Air Battery.

Highly stable and low-cost electrocatalysts with multi-electrocatalytic activities are in high demand for developing advanced energy conversion devices. Herein, a unique trifunctional amorphous iron-borate electrode is developed, which is capable of boosting hydrogen evolution, oxygen evolution, and oxygen reduction reactions simultaneously. The amorphous iron borate can self-assemble into well-defined nanolattices on electrode surface through a facile hydrothermal process, which possess more active sites and charge transfer pathways. As a result, the asymmetry overall water-splitting cell that adopts the amorphous electrodes as anode and cathode can be driven at 1.56 V with the current density of 10 mA cm-2 , which is lowest in state-of-the-art catalysts. Moreover, the water-splitting devices can be powered by a two-series-connected amorphous electrode-based zinc-air battery with high stability and Faradic efficiency (96.3%). The result can offer a potential and promising alternative way to develop metal-borate electrode for multifunctional applications.

Modulation in work function of CoTe as bifunctional electrocatalyst for rechargeable zinc air battery.

The sluggish kinetics and inferior stability of oxygen electrocatalyst in rechargeable zinc air battery (ZAB) hamper its industrialization. In this work, we activate cobalt telluride (CoTe) by introduction of metallic cobalt (Co) to modulate the work function to facilitate the electron transfer from Co to CoTe during oxygen catalysis; additionally, the three-dimensional porous carbon nanosheets (3DPC) are invited to reduce the resistance towards electrolyte/oxygen diffusion. Thereby, Co-CoTe@3DPC only demands 280 mV overpotential to reach 10 mA cm-2 under alkaline oxygen evolution reaction (OER) condition, relatively lower than commercial iridium oxides (IrO2); besides, the operando electrochemical impedance spectroscopy (EIS) indicates a better resistance towards surface reconstruction than Co@3DPC leading to a superior stability. A Pt-like oxygen reduction reaction (ORR) performance, half-wave potential associated with kinetic current density, is achieved for Co-CoTe@3DPC. A maximum power density of 203 mW cm-2 is achieved and sustains for 800 h. Furthermore, the all-solid-state ZAB offers 97 mW cm-2. Theoretical calculation suggests that the incorporation of metallic Co to CoTe maintains the superb ORR activity and promotes the OER catalysis.

In-Situ Nanoarchitectonics of Fe/Co LDH over Cobalt-Enriched N-Doped Carbon Cookies as Facile Oxygen Redox Electrocatalysts for High-Rate Rechargeable Zinc-Air Batteries.

The reality of long-term rechargeable and high-performance zinc-air batteries relies majorly on cost-effective and eminent bifunctional electrocatalysts, which can perform both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Herein, we demonstrate a new approach for the synthesis of in-situ-grown layered double hydroxide of iron and cobalt over a cobalt nanoparticle-enriched nitrogen-doped carbon frame (CoL 2:1) by a simple coprecipitation reaction with facile scale-up and explore its electrocatalytic ORR and OER activity for an electrically rechargeable zinc-air battery. Consequently, the developed composite displays excellent ORR and OER activity with an ORR half-wave potential of 0.84 V, a limiting current density of 5.85 mA/cm2, and an OER overpotential of 320 mV with exceptional stability. The outstanding bifunctionality index of the catalyst (ΔE = 0.72 V) inspired us to utilize it as a cathode catalyst in an in-house developed prototype zinc-air battery. The battery could easily supply a specific capacity of 804 mAh/g with a maximum peak power density of 161 mW/cm2. The battery exhibits an attractive charge-discharge profile with a lesser voltage gap of 0.76 V at 10 mA/cm2 with durability for a period of 200 h and a voltage efficiency of 97%, which surpassed the corresponding Pt/C + RuO2-based zinc-air battery. Further, a maximum load of 50 mA/cm2 could easily be sustained during cycling, revealing its outstanding stability. A series-connected two CoL 2:1-based zinc-air batteries effortlessly enlighten a pinwheel fan and LED panel simultaneously, revealing its practicality. The high electrical conductivity and greater specific surface area of Co/N-C and its robust attachment with Fe/Co LDH preserves both active sites, thereby resulting in exceptional performance. Our method is capable of being flexible enough to create various bifunctional Co/N-C-based composite electrodes, opening up a feasible pathway to rechargeable zinc-air batteries with maximum energy density.

Lignin-derived iron carbide/Mn, N, S-codoped carbon nanotubes as a high-efficiency catalyst for synergistically enhanced oxygen reduction reaction and rechargeable zinc-air battery.

Design of efficient and durable oxygen reduction reaction (ORR) electrocatalysts still remains challenge in sustainable energy storage and conversion devices. To achieve sustainable development, it is of importance to prepare high-quality carbon-derived ORR catalysts from biomass. Herein, Fe5C2 nanoparticles (NPs) were facilely entrapped in Mn, N, S-codoped carbon nanotubes (Fe5C2/Mn, N, S-CNTs) by a one-step pyrolysis of the mixed lignin, metal precursors and dicyandiamide. The resulting Fe5C2/Mn, N, S-CNTs had open and tubular structures, which exhibited positive shifts in the onset potential (Eonset = 1.04 V) and high half-wave potential (E1/2 = 0.85 V), showing excellent ORR characteristics. Further, the typical catalyst-assembled Zn-air battery showed a high power density (153.19 mW cm-2) and good cycling performance as well as obvious cost advantage. The research provides some valuable insights for rational construction of low-cost and environmentally sustainable ORR catalysts in clean energy field, coupled by offering some valuable insights for reusing biomass wastes.

FeNiCrCoMn High-Entropy Alloy Nanoparticles Loaded on Carbon Nanotubes as Bifunctional Oxygen Catalysts for Rechargeable Zinc-Air Batteries.

An efficient and stable bifunctional oxygen catalyst is necessary to complete the application of the rechargeable zinc-air battery. Herein, an economical and convenient process was adopted to successfully coat high-entropy alloy Fe12Ni23Cr10Co55-xMnx nanoparticles on carbon nanotubes (CNTs). In 0.1 M KOH solution, with a bifunctional oxygen overpotential (ΔE) of only 0.7 V, the catalyst Fe12Ni23Cr10Co30Mn25/CNT exhibits excellent bifunctional oxygen catalytic performance, exceeding most catalysts reported so far. In addition, the air electrode assembled with this catalyst exhibits high specific capacity (760 mA h g-1) and energy density (865.5 W h kg-1) in a liquid zinc-air battery, with a long-term cycle stability over 256 h. The density functional theory calculation points out that changing the atomic ratio of Co/Mn can change the adsorption energy of the oxygen intermediate (*OOH), which allows the ORR catalytic process to be accelerated in the alkaline environment, thereby increasing the ORR catalytic activity. This article has important implications for the progress of commercially available bifunctional oxygen catalysts and their applications in zinc-air batteries.

Engineering Fe-N4 Electronic Structure with Adjacent Co-N2C2 and Co Nanoclusters on Carbon Nanotubes for Efficient Oxygen Electrocatalysis.

Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement. Unlike the previously reported single-atom or dual-atom configurations, we designed a new type of binary-atom catalyst, through engineering Fe-N4 electronic structure with adjacent Co-N2C2 and nitrogen-coordinated Co nanoclusters, as oxygen electrocatalysts. The resultant optimized electronic structure of the Fe-N4 active center favors the binding capability of intermediates and enhances oxygen reduction reaction (ORR) activity in both alkaline and acid conditions. In addition, anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge- and mass-transports, and escorts the high bifunctional catalytic activity of the entire catalyst. Further, through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses, the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed. This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior. It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.

Cobalt Phthalocyanine-Doped Polymer-Based Electrocatalyst for Rechargeable Zinc-Air Batteries.

Rechargeable zinc-air batteries (RZAB) have gained significant attention as potential energy storage devices due to their high energy density, cost-effectiveness, and to the fact that they are environmentally safe. However, the practical implementation of RZABs has been impeded by challenges such as sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), including poor cyclability. Herein, we report the preparation of cobalt- and nitrogen-doped porous carbon derived from phloroglucinol-formaldehyde polymer networks with 2-methyl imidazole and cobalt phthalocyanine as precursors for nitrogen and cobalt. The CoN-PC-2 catalyst prepared in this study exhibits commendable electrocatalytic activity for both ORR and OER, evidenced by a half-wave potential of 0.81 V and Ej=10 of 1.70 V. Moreover, the catalyst demonstrates outstanding performance in zinc-air batteries, achieving a peak power density of 158 mW cm-2 and displaying excellent stability during charge-discharge cycles. The findings from this study aim to provide valuable insights and guidelines for further research and the development of hierarchical micro-mesoporous carbon materials from polymer networks, facilitating their potential commercialisation and widespread deployment in energy storage applications.

Construction of Co/FeCo@Fe(Co)3O4 heterojunction rich in oxygen vacancies derived from metal-organic frameworks using O2 plasma as a high-performance bifunctional catalyst for rechargeable zinc-air batteries.

Developing high-efficient, good-durability, and low-cost bifunctional non-precious metal catalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is urgent and significant for promoting the practical rechargeable zinc-air batteries (RZABs). Herein, N-doped carbon coated Co/FeCo@Fe(Co)3O4 heterojunction rich in oxygen vacancies derived from metal-organic frameworks (MOFs) is successfully constructed by O2 plasma treatment. The phase transition of Co/FeCo to FeCo oxide (Fe3O4/Co3O4) mainly occurs on the surface of nanoparticles (NPs) during the O2 plasma treatment, which can form rich oxygen vacancies simultaneously. The fabricated catalyst P-Co3Fe1/NC-700-10 with optimal O2 plasma treatment time of 10 min can reduce the potential gap between the OER and ORR to 760 mV, which is much lower than commercial 20% Pt/C + RuO2 (910 mV). Density functional theory (DFT) calculation indicates that the synergistic coupling between Co/FeCo alloy NPs and FeCo oxide layer can promote the ORR/OER performance. Both liquid electrolyte RZAB and flexible all-solid-state RZAB using P-Co3Fe1/NC-700-10 as the air-cathode catalyst display high power density, specific capacity and excellent stability. This work provides an effective idea for the development of high performance bifunctional electrocatalyst and the application of RZABs.

ZnS modified N, S dual-doped interconnected porous carbon derived from dye sludge waste as high-efficient ORR/OER catalyst for rechargeable zinc-air battery.

Facile and rational design of high-efficient oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysts is significant for rechargeable Zinc-air batteries. In this study, ZnS modified N, S dual-doped interconnected porous carbon (ZnS/NSC) derived from the dye sludge waste is successfully fabricated via a facile ZnCl2-assisted pyrolysis process. The effect of ZnCl2 and carbonization temperature on the microstructure and electrocatalytic performance is systematically investigated. By virtue of the synergistic effect between ZnS nanoparticles and N, S dual-doped porous carbon network, the obtained catalyst ZnS/NSC calcined at 1000 °C exhibits a decent bifunctional electrocatalytic performance with potential gap (ΔE=EOER,10-EORR,1/2) of 0.76 V comparable with commercial electrocatalysts (Pt/C and RuO2). In addition, a rechargeable zinc-air battery employed ZnS/NSC-1000 as the air cathode also displays the favorable electrochemical performance, in which the power density is 125 mW cm-2, the specific capacity is 763.27 mAh g-1 and the cycling stability at 10 mA cm-2 is more than 85 h, indicating a promising application prospect in rechargeable Zinc-air batteries.

Self-Assembly of Surface-Functionalized Ag1.8 Mn8 O16 Nanorods with Reduced Graphene Oxide Nanosheets as an Efficient Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

Bifunctional electrocatalysts play a key role in the performance of rechargeable metal-air batteries. Herein, we report a hybrid catalyst, Ag1.8 Mn8 O16 /rGO, self-assembled by Ag1.8 Mn8 O16 nanorods and reduced graphene oxide (rGO) nanosheets through electrostatic attraction. The hybrid catalyst exhibits a better oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity than commercial Pt/C in alkaline medium. When employed as an air-cathode catalyst in Zn-air cells, the hybrids enabled higher and more stable output voltage and better durability of the cells, benefitting from the improved electrode conductivity, larger surface area, and synergetic coupling as a result of its high structural integrity.

Fe-MOF-Derived Efficient ORR/OER Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

The construction of an efficient oxygen reduction reaction and oxygen evolution reaction (ORR/OER) bifunctional electrocatalyst is of great significance but still remains a giant challenge for high-performance metal-air batteries. In this study, uniform FeS/Fe3C nanoparticles embedded in a porous N,S-dual doped carbon honeycomb-like composite (abbr. FeS/Fe3C@NS-C-900) have been conveniently fabricated by pyrolysis of a single-crystal Fe-MOF, which has a low potential gap ΔE of ca. 0.72 V, a competitive power density of 90.9 mW/cm2, a specific capacity as high as 750 mAh/gZn, and excellent cycling stabilities over 865 h (1730 cycles) at 2 mA/cm2 when applied as a cathode material for rechargeable zinc-air batteries. In addition, the two series-linked Zn-air batteries successfully powered a 2.4 V LED light as a real power source. The efficient ORR/OER bifunctional electrocatalytic activity and long-term durability of the obtained composite might be attributed to the characteristic honeycomb-like porous structure with sufficient accessible active sites, the synergistic effect of FeS and Fe3C, and the N,S codoped porous carbon, which provides a promising application potential for portable electronic Zn-air battery related devices.

A Highly Efficient and Robust Cation Ordered Perovskite Oxide as a Bifunctional Catalyst for Rechargeable Zinc-Air Batteries.

Of the various catalysts that have been developed to date for high performance and low cost, perovskite oxides have attracted attention due to their inherent catalytic activity as well as structural flexibility. In particular, high amounts of Pr substitution of the cation ordered perovskite oxide originating from the state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) electrode could be a good electrode or catalyst because of its high oxygen kinetics, electrical conductivity, oxygen capacity, and structural stability. However, even though it has many favorable intrinsic properties, the conventional high-temperature treatment for perovskite synthesis, such as solid-state reaction and combustion process, leads to the particle size increase which gives rise to the decrease in surface area and the mass activity. Therefore, we prepared mesoporous nanofibers of various cation-ordered PrBa0.5Sr0.5Co2-xFexO5+δ (x = 0, 0.5, 1, 1.5, and 2) perovskites via electrospinning. The well-controlled B-site metal ratio and large surface area (∼20 m2 g-1) of mesoporous nanofiber result in high performance of the oxygen reduction reaction and oxygen evolution reaction and stability in zinc-air battery.