Revealing the Correlation of High-frequency Performance of Supercapacitors with Doped Nitrogen Species
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摘要: 氮掺杂炭材料已被广泛用于增强超级电容器的高频响应能力。然而，不同氮构型在高频下的电荷存储和离子响应机制仍不清楚。在本研究中，我们以具有开放表面结构的碳化三聚氰胺泡沫为简化模型材料，全面分析了N掺杂构型对超级电容器高频响应行为的影响。结合实验和第一性原理计算，我们发现具有较高吸附能的吡咯氮可以增强高频下炭电极的电荷存储能力。而具有较低吸附能的石墨氮则有助于离子在高频下的快速响应。此外，我们提出吸附能可作为高频下电极/电解界面设计的描述符，这为优化氮掺杂炭材料的高频性能提供了更普遍的方法。这些结果为开发用于高频超级电容器的氮掺杂炭材料提供了指导。Abstract: Nitrogen doping has been widely used to enhance the performance of carbon electrodes in supercapacitors, particularly in terms of high-frequency response. However, the charge storage and ion response mechanisms of different nitrogen species at high frequencies is still unclear. In this study, we employ carbonized melamine foam with open surface structure as a simplified model material, enabling a comprehensive analysis of their impact on the ionic response behavior of high-frequency supercapacitors. Through a combination of experiments and first-principles calculations, we uncover that pyrrolic nitrogen, characterized by a higher adsorption energy, enhances the charge storage capacity of the electrode at high frequencies. On the other hand, graphitic nitrogen, with a lower adsorption energy, promotes rapid ion response. Furthermore, we propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications, offering a more universal approach for optimizing the performance of N-doped carbon materials. This research contributes to the advancement of high-frequency supercapacitor technology and provides guidance for the development of improved N-doped carbon materials.
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Figure 1. Morphology characterizations of the CMF. (a) Molecular structure diagram of melamine resin. (b) Digital photos of a piece of melamine foam before and after carbonization. (c) SEM images of CMF-1000. (d) The corresponding elemental mapping of CMF-1000
Figure 2. Structure characterizations of the CMF. (a) N2 adsorption-desorption isotherms. (b) Pore size distribution isotherms. (c) Raman spectra. First-order Raman spectrum fitting curve of (d) CMF-800, (e) CMF-900, and (f) CMF-1000
Figure 3. The molecular structure and chemical state of N element in CMF. (a) XRD patterns. (b) FT-IR spectrum. (c) XPS surveys. High-resolution N 1s spectra of (d) CMF-800, (e) CMF-900 and (e) CMF-1000
Figure 4. The performance of CMF in 1 M Na2SO4 electrolyte. (a) CV curves at 2000 V s−1, (b) Plots of discharge current density versus scan rate, (c) Nyquist complex impedance spectrum, (d) Bode phase diagram, (e) the variation of Cm, (f)
$ {{C}}'' $ versus frequency based on series-RC circuit model
Figure 5. The performance of CMF in SBPBF4/AN electrolyte. (a) CV curves at 2000 V s−1, (b) Plots of discharge current density versus scan rate, (c) Nyquist complex impedance spectrum, (d) Bode phase diagram, (e) the variation of Cm, (f)
$ {{C}}'' $ versus frequency
Figure 6. The DFT simulations of various N-doped carbon surfaces. The charge density difference of N-doped carbon surface after ion adsorption with (a) pyridinic nitrogen, (b) pyrrolic nitrogen, and (c) graphitic nitrogen, respectively
Figure 7. (a) The adsorption energy of Na+, SBP+, TEA+, and EMIM+ on various N-doped carbon surfaces. The linear correlation of −Eads with (b) f0, (c) Cm,120 Hz, and (d) τ0, respectively
Table 1. Element analysis of CMF-800, CMF-900, and CMF-1000 by XPS
Sample Elemental content (at. %) C 1s N 1s O 1s CMF-800 87.36 4.62 8.03 CMF-900 88.52 4.04 7.44 CMF-1000 90.26 3.43 6.31 
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Table 2. N 1s of CMF-800, CMF-900 and CMF-1000
Sample The relative content of nitrogen configurations (at. %) Pyridinic Pyrrolic Graphitic Oxidized CMF-800 47.03 34.08 4.99 13.90 CMF-900 30.19 43.10 10.78 13.08 CMF-1000 19.42 27.30 36.65 14.79
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