钴单原子位点对碳基超级电容器电极倍率性能的动力学提升

Cobalt Single-atom Sites for Kinetically Enhanced Rate Performance of Carbon-based Supercapacitor Electrodes

摘要

为揭示相邻过渡金属单原子位点对碳基超级电容器电极储能动力学的影响, 以活性炭为碳基底, 通过金属-配体配位及碳化策略制备了Fe和Co两种金属单原子修饰氮掺杂碳材料(M@NC), 并以不含金属单原子位点的NC作为对照样品. 结构表征表明, NC, Fe@NC 和Co@NC 具有相近的碳基结构和孔结构特征; Fe和Co物种均以高度分散状态锚定于氮掺杂碳基体中, 形成M-N₄配位结构. 电化学测试结果显示, Fe@NC和Co@NC相较于NC具有更高的比电容, 说明金属单原子位点的引入能够改善碳基电极的储能行为. Fe@NC和Co@NC在1 A/g电流密度下表现出相近的比电容, 分别为106和109 F/g; 当电流密度提升至20 A/g时, Co@NC的电容保持率为55%, 明显高于Fe@NC的38%, 说明Co单原子位点更有利于改善碳基电极的高倍率电容保持能力. 动力学分析表明, Co@NC具有较高的电容控制贡献比例、 更低的电荷转移阻抗和更优的离子扩散特征, 表明Co单原子位点更有利于快速电荷/离子传输过程. 研究结果表明, 金属单原子位点对碳基超级电容器电极倍率性能的提升主要源于电化学动力学优化, 其中Co单原子位点在促进快速储能方面更具优势. 本研究为单原子位点调控碳基超级电容器电极材料倍率性能提供了科学依据.

Abstract

To elucidate the influence of adjacent transition-metal single-atom sites on the energy-storage kinetics of carbon-based supercapacitor electrodes, Fe and Co single-atom-modified nitrogen-doped carbon materials, denoted as Fe@NC and Co@NC, were prepared using activated carbon as the carbon substrate via a metal-ligand coordination and carbonization strategy. Nitrogen-doped carbon without metal single-atom sites was used as the control sample. Structural characterizations reveal that NC, Fe@NC, and Co@NC possess similar carbon frameworks and porous structures, while Fe and Co species are highly dispersed and anchored in the nitrogen-doped carbon matrix, forming M-N₄ coordination configurations. Electrochemical measurements show that Fe@NC and Co@NC deliver higher specific capacitances than NC, indicating that the introduction of metal single-atom sites can improve the charge-storage capability of carbon-based electrodes. Fe@NC and Co@NC exhibit comparable specific capacitances at current density of 1 A/g, with values of 106 and 109 F/g, respectively. When the current density increases to 20 A/g, Co@NC retains 55% of its capacitance, markedly higher than Fe@NC (38%), suggesting that Co single-atom sites are more favorable for improving high-rate capacitance retention. Further kinetic analyses demonstrate that Co@NC possesses a higher capacitive-controlled contribution, lower charge-transfer resistance, and more favorable ion-diffusion behavior, indicating that Co single-atom sites are more effective in facilitating rapid charge/ion transport. These results reveal that the rate-performance enhancement of carbon-based supercapacitor electrodes induced by metal single-atom sites mainly originates from optimized electrochemical kinetics, with Co single-atom sites showing greater advantages in promoting fast energy storage. This study provides mechanistic insight into the regulation of rate performance in carbon-based supercapacitor electrodes through single-atom site engineering.

关键词

单原子 / 碳基电极材料 / 超级电容器 / 电化学动力学 / 倍率性能

Key words

Single atom / Carbon-based electrode material / Supercapacitor / Electrochemical kinetics / Rate performance

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基金资助

重庆市自然科学基金(CSTB2022NSCQ-MSX1101)