This study investigates three carbide-derived carbon (CDC) materials (TiC, NbC, and Mo2C) characterized by uni-, bi-, and tri-modal pore sizes, respectively, for energy storage in both neat and acetonitrile-diluted 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A distribution of micro- and mesopores was studied through low-temperature N2 and CO2 adsorption. To elucidate the relationships between porosity and the electrochemical properties of carbon materials, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy measurements were conducted using three-electrode test cells. The ultramicroporous TiC-derived carbon is characterized by a high packing density of 0.85 g cm−3, resulting in superior cathodic and anodic capacitances for both neat ionic liquid (IL) and a 1.9 M IL/acetonitrile electrolyte (93.6 and 75.8 F cm−3, respectively, in the dilute IL). However, the bi-modal pore-sized microporous NbC-derived carbon, with slightly lower cathodic and anodic capacitances (i.e., 85.0 and 73.7 F cm−3 in the dilute IL, respectively), has a lower pore resistance, making it more suitable for real-world applications. A symmetric two-electrode capacitor incorporating microporous CDC-NbC electrodes revealed an acceptable cycle life. After 10,000 cycles, the cell retained approximately 75% of its original capacitance, while the equivalent series resistance (ESR) only increased by 13%.
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.
The development of non-precious metal electrocatalysts towards oxygen reduction reaction (ORR) is crucial for the commercialisation of polymer electrolyte fuel cells. In this work, cobalt-containing nitrogen-doped porous carbon materials were prepared by a pyrolysis of mixtures of saccharides, cobalt nitrate and dicyandiamide, which acts as a precursor for reactive carbon nitride template and a nitrogen source. The rotating disk electrode (RDE) experiments in 0.1 M KOH solution showed that the glucose-derived material with optimised cobalt content had excellent ORR activity, which was comparable to that of 20 wt% Pt/C catalyst. In addition, the catalyst exhibited high tolerance to methanol, good stability in short-time potential cycling test and low peroxide yield. The materials derived from xylan, xylose and cyclodextrin displayed similar activities, indicating that various saccharides can be used as inexpensive and sustainable precursors to synthesise active catalyst materials for anion exchange membrane fuel cells.
We explored two methods for synthesizing Pd nanoparticles using three different carbide-derived carbon (CDC) support materials, one of which was nitrogen-doped. These materials were studied for oxygen reduction reaction (ORR) in 0.1 M KOH solution, and the resulting CDC/Pd catalysts were characterized using TEM, XRD, and XPS. The citrate method and the polyol method using polyvinylpyrrolidone (PVP) as a capping agent were employed to elucidate the impact of the support material on the final catalyst. The N-doping of the CDC material resulted in smaller Pd nanoparticles, but only in the case of the citrate method. This suggests that the influence of support is weaker when using the polyol method. The citrate method with CDC1, which is predominantly microporous, led to a higher degree of agglomeration and formation of larger particles in comparison to supports, which possessed a higher degree of mesoporosity. We achieved smaller Pd particle sizes using citrate and NaBH4 compared to the ethylene glycol PVP method. Pd deposited on CDC2 and CDC3 supports showed similar specific activity (SA), suggesting that the N-doping did not significantly influence the ORR process. The highest SA value was observed for CDC1/Pd_Cit, which could be attributed to the formation of larger Pd particles and agglomerates.