Hollow Co3O4 Nanosphere Embedded in Carbon Arrays for Stable and Flexible Solid‐State Zinc–Air Batteries

Highly active and durable air cathodes to catalyze both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are urgently required for rechargeable metal–air batteries. In this work, an efficient bifunctional oxygen catalyst comprising hollow Co₃O₄ nanospheres embedded in nitrogen‐doped carbon nanowall arrays on flexible carbon cloth (NC‐Co₃O₄/CC) is reported. The hierarchical structure is facilely derived from a metal–organic framework precursor. A carbon onion coating constrains the Kirkendall effect to promote the conversion of the Co nanoparticles into irregular hollow oxide nanospheres with a fine scale nanograin structure, which enables promising catalytic properties toward both OER and ORR. The integrated NC‐Co₃O₄/CC can be used as an additive‐free air cathode for flexible all‐solid‐state zinc–air batteries, which present high open circuit potential (1.44 V), high capacity (387.2 mAh g^?1, based on the total mass of Zn and catalysts), excellent cycling stability and mechanical flexibility, significantly outperforming Pt‐ and Ir‐based zinc–air batteries.     

Integrated Hierarchical Carbon Flake Arrays with Hollow P‐Doped CoSe2 Nanoclusters as an Advanced Bifunctional Catalyst for Zn–Air Batteries

Hierarchical nanostructured architectures are demonstrated as an effective approach to develop highly active and bifunctional electrocatalysts, which are urgently required for efficient rechargeable metal–air batteries. Herein, a mesoporous hierarchical flake arrays (FAs) structure grown on flexible carbon cloth, integrated with the microsized nitrogen‐doped carbon (N‐doped C) FAs, nanoscaled P‐doped CoSe₂ hollow clusters and atomic‐level P‐doping (P‐CoSe₂/N‐C FAs) is described. The P‐CoSe₂/N‐C FAs thus developed exhibit a reduced overpotential (≈230 mV at 10 mA cm^?2) toward oxygen evolution reaction (OER) and large half‐wave potential (0.87 V) for oxygen reduction reactions. The excellent bifunctional electrocatalytic performance is ascribed to the synergy among the hierarchical flake arrays controlled at both micro‐ and nanoscales, and atomic‐level P‐doping. Density functional theory calculations confirm that the free energy for the potential‐limiting step is reduced by P‐doping for OER. An all‐solid‐state zinc–air battery made of the P‐CoSe₂/N‐C FAs as the air‐cathode presents excellent cycling stability and mechanical flexibility, demonstrating the great potential of the hierarchical P‐CoSe₂/N‐C FAs for advanced bifunctional electrocatalysis.     

Investigation of Charge Transfer Kinetics of Polyaniline Supercapacitor Electrodes by Scanning Electrochemical Microscopy

Scanning Electrochemical Microscopy (SECM) is introduced as a promising technique to probe localized interfacial kinetics at the interface of electrolyte/supercapacitor electrode based on polyaniline (PANI) by measuring approach curves from which heterogeneous charge transfer rate constants (k _eff) are extracted. The values correlate with the effectiveness of the electrode material for supercapacitor application. Specifically, measurements on PANI films of different thicknesses show that potential‐dependent rate constants are observed only for PANI films of up to 5 μm thickness. In addition to the thickness of PANI, k _eff is also found to be affected by the applied potential and surface morphology of PANI electrodes. These findings correlate with the macroscopic electrochemical performance of PANI electrodes which shows enhanced specific charge storage ability when their thickness is below 5 μm. Under these conditions, they deliver a specific capacitance of 486 F g⁻¹ and a rate capability of 89%. The observed correlation between microscopic kinetic data determined by SECM and macroscopic device characteristics provides rational guidelines for the optimization of the physical and structural properties of high performance supercapacitor electrodes.