skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Porous FeCo Glassy Alloy as Bifunctional Support for High‐Performance Zn‐Air Battery
Abstract The Zn‐air battery (ZAB) is attracting increasing attention due to its high safety and preeminent performance. However, the practical application of ZAB relies heavily on developing durable support materials to replace conventional carbon supports which have unrecoverable corrosion issues, severely jeopardizing ZAB performance. Herein, a novel porous FeCo glassy alloy is developed as a bifunctional catalytic support for ZAB. The conducting skeleton of the porous glassy alloy is used to stabilize oxygen reduction cocatalysts, and more importantly, the FeCo serves as the primary phase for oxygen evolution. To demonstrate the concept of catalytic glassy alloy support, ultrasmall Pd nanoparticles are anchored, as oxygen reduction active sites, on the porous FeCo (noted as Pd/FeCo) for ZAB. The Pd/FeCo exhibits a significantly improved electrocatalytic activity for oxygen reduction (a half‐wave potential of 0.85 V) and oxygen evolution (a potential of 1.55 V to reach 10 mA cm−2) in the alkaline media. When used in the ZAB, the Pd/FeCo delivers an output power density of 117 mW cm−2and outstanding cycling stability for over 200 h (400 cycles), surpassing the conventional carbon‐supported Pt/C+IrO2catalysts. Such an integrated design that combines highly active components with a porous architecture provides a new strategy to develop novel nanostructured electrocatalysts.  more » « less
Award ID(s):
1851674
PAR ID:
10454737
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Energy Materials
Volume:
11
Issue:
3
ISSN:
1614-6832
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Developing high performance nonprecious metal‐based electrocatalysts has become a critical first step towards commercial applications of metal‐air batteries. Herein, nanocomposites based on Co/Co2P nanoparticles encapsulated within hierarchically porous N, P, S co‐doped carbon are prepared by controlled pyrolysis of zeolitic imidazolate frameworks (ZIF‐67) and poly(cyclotriphosphazene‐co‐4,4’‐sulfonyldiphenol) (PZS). The resulting Co/Co2P@NPSC nanocomposites exhibit apparent oxygen reduction reaction (ORR) and evolution reaction (OER) catalytic performance, and are used as the reversible oxygen catalyst for zinc‐air batteries (ZABs). Density functional theory (DFT) calculations exhibit that Co2P could provide active sites for the ORR and promote the conversion between the adsorbed intermediates, and porous N,P,S co‐doped carbon with Co2P nanoparticles also improves the exposure of actives sites and endows charge transport. Liquid‐state ZABs with Co/Co2P@NPSC as the cathode catalysts demonstrate the greater power density of 198.1 mW cm−2and a long cycling life of 50 h at 10 mA cm−2, likely due to the encapsulation of Co/Co2P nanoparticles by the carbon shell. Solid‐state ZABs also display a remarkable performance with a high peak power density of 74.3 mW cm−2. Therefore, this study indicates the meaning of the design and engineering of hierarchical porous carbon nanomaterial as electrocatalyst for rechargeable metal‐air batteries. 
    more » « less
  2. Employing the strong metal-support interaction (SMSI) effect for promoting the catalyst's activity toward the oxygen reduction reaction (ORR) is promising due to the electronic structure optimization and high utilization efficiency of platinum group metal (PGM) catalysts. Metal oxides as alternative supports for PGMs facilitate intrinsic activity and improve durability as compared to conventional carbon supports. However, the restricted mass and electron transfer at the metal/support interface need to be addressed. Herein, to strengthen the interaction at the metal/support interfaces and improve the utilization efficiency of PGM, an ultralow loading of Pd was embedded in a surface-oxygenated PdNiMnO porous film. The Mn-doping was designed to promote surface oxygenation using a facile anodization process that created sufficiently exposed interfaces between Pd and the support, strengthening the SMSI effects at the Pd/oxygenated support interface for enhancing ORR performance. Furthermore, the Ni-containing oxygenated catalyst served as both the active component for the oxygen evolution reaction (OER) and the functional support for stabilizing Pd, making PdNiMnO a bifunctional catalyst for zinc–air flow batteries (ZAFB). As a proof-of-concept, the ZAFB (PdNiMnO) shows a maximal power density of 211.6 mW cm −2 and outstanding cycling stability for over 2000 h with a minimal voltage gap of 0.69 V at a current density of 10 mA cm −2 , superior to the state-of-the-art catalysts. 
    more » « less
  3. Abstract Porous electrodes that conduct electrons, protons, and oxygen ions with dramatically expanded catalytic active sites can replace conventional electrodes with sluggish kinetics in protonic ceramic electrochemical cells. In this work, a strategy is utilized to promote triple conduction by facilitating proton conduction in praseodymium cobaltite perovskite through engineering non‐equivalent B‐site Ni/Co occupancy. Surface infrared spectroscopy is used to study the dehydration behavior, which proves the existence of protons in the perovskite lattice. The proton mobility and proton stability are investigated by hydrogen/deuterium (H/D) isotope exchange and temperature‐programmed desorption. It is observed that the increased nickel replacement on the B‐site has a positive impact on proton defect stability, catalytic activity, and electrochemical performance. This doping strategy is demonstrated to be a promising pathway to increase catalytic activity toward the oxygen reduction and water splitting reactions. The chosen PrNi0.7Co0.3O3−δoxygen electrode demonstrates excellent full‐cell performance with high electrolysis current density of −1.48 A cm−2at 1.3 V and a peak fuel‐cell power density of 0.95 W cm−2at 600 °C and also enables lower‐temperature operations down to 350 °C, and superior long‐term durability. 
    more » « less
  4. Abstract The development of dual catalysts with high efficiency toward oxygen reduction and evolution reactions (ORR and OER) in acidic media is a significant challenge. Here an active and durable dual catalyst based upon cubic Pt39Ir10Pd11nanocages with an average edge length of 12.3 nm, porous walls as thin as 1.0 nm, and well‐defined {100} facets is reported. The trimetallic nanocages perform better than all the reported dual catalysts in acidic media, with a low ORR‐OER overpotential gap of only 704 mV at a Pt‐Ir‐Pd loading of 16.8 µgPt+Ir+Pdcm−2geo. For ORR at 0.9 V, when benchmarked against the commercial Pt/C and Pt‐Pd nanocages, the trimetallic nanocages exhibit an enhanced mass activity of 0.52 A mg−1Pt+Ir+Pd(about four and two times as high as those of the Pt/C and Pt‐Pd nanocages) and much improved durability. For OER, the trimetallic nanocages show a remarkable mass activity of 0.20 A mg−1Pt+Irat 1.53 V, which is 16.7 and 4.3 fold relative to those of the Pt/C and Pt‐Pd nanocages, respectively. These improvements can be ascribed to the highly open structure of the nanocages, and the possible electronic coupling between Ir and Pt atoms in the lattice. 
    more » « less
  5. Abstract It is essential but still challenging to design and construct inexpensive, highly active bifunctional oxygen electrocatalysts for the development of high power density zinc–air batteries (ZABs). Herein, a CoFe‐S@3D‐S‐NCNT electrocatalyst with a 3D hierarchical structure of carbon nanotubes growing on leaf‐like carbon microplates is designed and prepared through chemical vapour deposition pyrolysis of CoFe‐MOF and subsequent hydrothermal sulfurization. Its 3D hierarchical structure shows excellent hydrophobicity, which facilitates the diffusion of oxygen and thus accelerates the oxygen reduction reaction (ORR) kinetic process. Alloying and sulfurization strategies obviously enrich the catalytic species in the catalyst, including cobalt or cobalt ferroalloy sulfides, their heterojunction, core–shell structure, and S, N‐doped carbon, which simultaneously improve the ORR/OER catalytic activity with a small potential gap (ΔE = 0.71 V). Benefiting from these characteristics, the corresponding liquid ZABs show high peak power density (223 mW cm−2), superior specific capacity (815 mA h gZn−1), and excellent stability at 5 mA cm−2for ≈900 h. The quasi‐solid‐state ZABs also exhibit a very high peak power density of 490 mW cm−2and an excellent voltage round‐trip efficiency of more than 64%. This work highlights that simultaneous composition optimization and microstructure design of catalysts can effectively improve the performance of ZABs. 
    more » « less