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Abstract In this work, an organic‐inorganic hybrid crystal, violet‐crystal (VC), was used to etch the nickel foam (NF) to fabricate a self‐standing electrode for the water oxidation reaction. The efficacy of VC‐assisted etching manifests the promising electrochemical performance towards the oxygen evolution reaction (OER), requiring only ~356 and ~376 mV overpotentials to reach 50 and 100 mA cm−2, respectively. The OER activity improvement is attributed to the collectively exhaustive effects arising from the incorporation of various elements in the NF, and the enhancement of active site density. Furthermore, the self‐standing electrode is robust, exhibiting a stable OER activity after 4,000 cyclic voltammetry cycles, and ~50 h. The anodic transfer coefficients (αa) show that the first electron transfer step is the rate‐determining step on the surface of NF‐VCs‐1.0 (NF etched by 1 g of VCs) electrode, while the chemical step involving dissociation following the first electron transfer step is identified as the rate‐limiting step in other electrodes. The lowest Tafel slope value observed in the NF‐VCs‐1.0 electrode indicates the high surface coverage of oxygen intermediates and more favorable OER reaction kinetics, as confirmed by high interfacial chemical capacitance and low charge transport/interfacial resistance. This work demonstrates the importance of VCs‐assisted etching of NF to activate the OER, and the ability to predict reaction kinetics and rate‐limiting step based onαavalues, which will open new avenues to identify advanced electrocatalysts for the water oxidation reaction.
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Influence of Finite Diffusion on Cation Insertion-Coupled Electron Transfer Kinetics in Thin Film Electrodes
Materials that undergo ion-insertion coupled electron transfer are important for energy storage, energy conversion, and optoelectronics applications. Cyclic voltammetry is a powerful technique to understand electrochemical kinetics. However, the interpretation of the kinetic behavior of ion insertion electrodes with analytical solutions developed for ion blocking electrodes has led to confusion about their rate-limiting behavior. The purpose of this manuscript is to demonstrate that the cyclic voltammetry response of thin film electrode materials undergoing solid-solution ion insertion without significant Ohmic polarization can be explained by well-established models for finite diffusion. To do this, we utilize an experimental and simulation approach to understand the kinetics of Li+insertion-coupled electron transfer into a thin film material (Nb2O5). We demonstrate general trends for the peak current vs scan rate behavior, with the latter parameter elevated to an exponent between limiting values of 1 and 0.5, depending on the solid-state diffusion characteristics of the film (diffusion coefficient, film thickness) and the experiment timescale (scan rate). We also show that values < 0.5 are possible depending on the cathodic potential limit. Our results will be useful to fundamentally understand and guide the selection and design of intercalation materials for multiple applications.
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- Award ID(s):
- 1653827
- PAR ID:
- 10487433
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 171
- Issue:
- 1
- ISSN:
- 0013-4651
- Format(s):
- Medium: X Size: Article No. 010527
- Size(s):
- Article No. 010527
- Sponsoring Org:
- National Science Foundation
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