RESUMO
Efficient and durable bifunctional catalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are urgently desirable but challenging for rechargeable Zn-air batteries (ZABs), especially flexible wearable ZABs. Inspired by the vine-leaf-whisker structure in nature, we proposed a three-dimensional (3D) hierarchical bifunctional catalyst (denoted as Co-Fe-Zn@N-CNT/CNF) consisting of N-doped carbon nanotubes embedded with abundant CoFe alloy nanoparticles, leaf-shaped N-doped carbon nanoflakes, and porous carbon fibers for rechargeable ZABs. The special biomimetic structure provides a large specific surface area, allowing for high exposure of the active site and ensuring fast mass transport/charge transfer. The close combination of CoFe bimetallic alloys and N-doped carbon nanotubes delivers high electrocatalytic activity, while the coexistence of various active sites such as metal nanoparticles (NPs), metal-Nx, doped N species, and their synergistic interactions endows the catalysts with more active sites. As such, the Co-Fe-Zn@N-CNT/CNF catalyst achieves superior bifunctional catalytic activities for the ORR (a half-wave potential of 0.84 V) and the OER (an overpotential of 326 mV at 10 mA cm-2) in alkaline media, comparable to commercial Pt/C and RuO2. Remarkably, both aqueous and solid-state ZABs assembled with Co-Fe-Zn@N-CNT/CNF catalysts as air electrodes demonstrate excellent charging/discharging performance, high peak power density, and robust long-term cycling stability. More interestingly, the flexible ZAB performs well even under bending conditions, displaying satisfactory device stability and mechanical flexibility. This study presents a new collective morphological-composition-structural engineering strategy for exploiting the efficient bifunctional oxygen electrocatalysts, which is of great significance for high-performance rechargeable ZABs and wearable energy storage devices.
RESUMO
Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) have attracted growing attention in electrochemical energy storage and conversion systems (e.g., Zn-air batteries, ZABs) owing to their structural tunability, ordered porosity and high specific surface area. In this work, for the first time, the three-dimensional (3D) highly open catalyst (CNFs/CoZn-MOF@COF) possessing hierarchical porous structure and high-density active sites of uniform cobalt (Co) nanoparticles and metal-Nx (M-Nx, M = Co and Zn) is demonstrated, which is fabricated using electrospinning technique in combination with MOF/COF hybridization strategy and direct pyrolysis. Benefiting from the well-designed branch-leaf nanostructures, plentiful and uniform active sites on the MOF/COF-derived carbon frameworks, as well as the synergistic effect of multiple active sites, CNFs/CoZn-MOF@COF catalyst achieves superior electrocatalytic activity and stability towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with a small potential gap (ΔE = 0.75 V). In situ Raman spectroscopy and X-ray photoelectron spectroscopy results indicate that the CoOOH intermediates are the main active species during OER/ORR. Significantly, both aqueous and all-solid-state rechargeable ZABs assembled with CNFs/CoZn-MOF@COF as the air cathode show high open-circuit potential, outstanding peak power density, large capacity and long cycle life. More impressively, the obtained all-solid-state ZAB also displays superb mechanical flexibility and device stability under different, showcasing great application deformations potential in portable and wearable electronics. This work provides a new insight into the design and exploitation of bifunctional catalysts from MOF/COF hybrid materials for energy storage and conversion devices.
RESUMO
Atomic-level modulation of the metal-oxide interface is considered an effective approach to optimize the electronic structure and catalytic activity of metal catalysts but remains highly challenging. Here, we employ the atomic layer deposition (ALD) technique together with a heteroatom doping strategy to effectively tailor the electronic metal-support interaction (EMSI) at the metal-oxide interface on the atomic level, thereby achieving high hydrogen evolution performance and Pt utilization. Theoretical calculations reveal that the doping of N atoms in Co3O4 significantly adjusts the EMSI between Pt-Co3O4 interfaces and, consequently, alters the d-band center of Pt and optimizes the adsorption/desorption of reaction intermediates. This work sheds light on the atomic-level regulation and mechanistic understanding of the EMSI in metal-oxide, while providing guidance for the development of advanced EMSI electrocatalysts for various future energy applications.
RESUMO
Exploiting the high-entropy alloy (HEA) electrocatalysts with the synergistic effect of multi-metal components is an effective approach to address the slow kinetics and undesirable stability of the oxygen evolution reaction (OER) in Zn-air batteries (ZABs), but still faces many challenges. In this study, a multimetallic Metal-organic framework (MOF)-derived HEA catalyst was successfully fabricated on carbon fiber as a flexible self-supporting electrode (denoted as CC@FeCoNiMoRu-HEA/C) for high-performance liquid/flexible ZABs using a facile and cost-effective strategy. The three-dimensional (3D) highly open network framework and hierarchical porous structure accelerate the mass transport of OH-/O2 and charge transfer. The electronic structure adjustment, lattice defects and high entropy effects enable the CC@FeCoNiMoRu-HEA/C catalysts to perform high OER catalytic activity and strong durability while reducing the Ru content and lowering the economic cost. In situ Raman spectra and XPS results reveal the generation of metal-OOH intermediates on the HEA surface during the OER process. In a practical demonstration, the liquid ZAB assembled with CC@FeCoNiMoRu-HEA/C + Pt/C as the air electrode offers stable open-circuit voltage, large power density, excellent specific capacity and satisfactory cycle life, outperforming the commercial RuO2 + Pt/C-based reference ZAB. More attractively, the flexible solid-state ZAB also achieves fast dynamic response, high peak power density, robust cycling stability as well as favorable mechanical flexibility, indicating a promising application prospect in future flexible electronics and wearable devices. This work provides a viable pathway to develop low precious metal-loaded HEAs as advanced OER self-supporting electrocatalysts and realize high-performance flexible energy storage devices.