富碳氮化碳全固态光超级电容器性能影响因素研究

doi:10.6023/A25010031

摘要/Abstract

储能技术对于稳定未来智能电网尤为重要. 全固态储能技术仍是推动储能系统发展的关键挑战. 本工作利用富碳氮化碳(CPCN)本征具有光吸收和电荷存储的双重功能和TiO₂高介电性制备出不含电解质的全固态光超级电容器. 为提高富碳氮化碳全固态光超级电容器的光生电荷存储容量, 对其性能影响因素进行研究. 通过延长CPCN熟化时间、提高TiO₂介孔薄膜的厚度、增大TiO₂/CPCN电极面积使光生电荷存储容量显著增加. 并且串联模式下可以有效增大电压窗口, 并联模式下可以进一步减少电子损失, 光生电荷存储容量达到412.8 C•g^-1.

关键词: 富碳氮化碳, 共轭聚合物, 全固态光超级电容器, 光生电荷存储, 太阳能

Energy storage technology is particularly important for stabilizing smart grids for the future. All-solid-state energy storage remains a critical challenge for advancing energy storage systems. Carbon nitride conjugated polymers have the greatest development potential due to their special direct photogenerated charge storage behavior. We successfully fabricated an electrolyte-free, all-solid-state photo-supercapacitor based on carbon-rich carbon nitride, comprising a C-rich carbon nitride conjugated polymer (CPCN), TiO₂ nanocrystals, and fluorine-doped tin oxide (FTO) conductive glass. The device structure follows the configuration FTO//TiO₂//CPCN//TiO₂//FTO, where CPCN functions as the light-absorbing layer for photogenerated carrier generation and charge storage, while TiO₂ serves as both charge stabilization and transport material. Material morphology was characterized by scanning electron microscopy (SEM), and the composition was analyzed by element distribution map equipped with SEM. Photoelectrochemical performance and charge storage behavior were systematically evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) measurements, and electrochemical impedance spectroscopy (EIS). The optimal CPCN aging time, TiO₂ mesoporous film thickness and TiO₂/CPCN electrode area were found to make the photogenerated charge storage capacity of the single cell reach 380.1 C•g^-1. It was also found that the specific capacity of the battery was stable at a constant level between 350.7 C•g^-1 and 340.3 C•g^-1 when the electrode area exceeded 9 cm^-2. The energy management concept of the photo-supercapacitor to store photogenerated electrons first and then release them can avoid the problem of photoelectric conversion performance degradation caused by the increase in size like photovoltaic cells. In parallel mode, the photoelectric synergistic effect of CPCN can further reduce electron loss, and the photo charge storage capacity is significantly improved to 412.8 C•g^-1, and the performance does not decay with the increase in battery size. C-rich carbon nitride-based all-solid-state photo-supercapacitors use solar energy to achieve efficient, stable, safe, easy-to-control, low-carbon and environmentally friendly all-solid-state energy storage. The device has broad application prospects in the fields of solar energy management, visual energy storage equipment and self-powered sensors in smart grids.

Key words: C-rich carbon nitride, conjugated polymer, all-solid-state photo-supercapacitor, photogenerated charge storage, solar energy

引用此文

曾玥, 唐笑, 周于芝, 李艳虹, 荆川, 凌发令, 杨红梅, 周贤菊. 富碳氮化碳全固态光超级电容器性能影响因素研究[J]. 化学学报, 2025, 83(5): 488-497.

Yue Zeng, Xiao Tang, Yuzhi Zhou, Yanhong Li, Chuan Jing, Faling Ling, Hongmei Yang, Xianju Zhou. Study on Factors Affecting Performance of C-Rich Carbon Nitride-based All-Solid-State Photo-Supercapacitor[J]. Acta Chimica Sinica, 2025, 83(5): 488-497.

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图/表 8

图1. (a) CPCN样品的SEM图; (b) CPCN局部SEM图和SEM-EDS元素映射图; (c) CPCN冻干粉末; (d) TiO2纳米晶薄膜; (e)电池图片; (f)电池组装流程图

Figure 1. (a) SEM image of the CPCN sample; (b) CPCN local SEM diagram and SEM-EDS element mapping; (c) Lyophilized CPCN powder; (d) TiO₂ nanocrystal films; (e) Pictures of the battery; (f) Schematic diagram of device fabrication process

图2. (a) 工作状态下照片; (b) 不同熟化时间CPCN样品的CV曲线; EIS测试结果: (c) 熟化1个月(CN1); (d) 熟化3个月(CN3); (e) 熟化8个月(CN8); (f) 熟化10个月(CN10); (g) 拟合的Rct值; 不同熟化时间CPCN样品的光超级电容器光生电荷存储性能: (h) 光生电荷存储容量; (i) 库伦效率. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 2. (a) Operational state photograph; (b) CV curves of CPCN samples with different maturation times; EIS test results: (c) 1 month of maturation (CN1); (d) 3 months of maturation (CN3); (e) 8 months of maturation (CN8); (f) 10 months of maturation (CN10); (g) Fitted Rct values; Photogenerated charge storage performance of photo-supercapacitors in CPCN samples with different maturation times: (h) Photogenerated charge storage capacity; (i) Coulombic efficiency. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

图3. TiO2/CPCN电极的表征: (a) SEM正面图; (b) SEM横截面图; (c) 横截面SEM-EDS元素映射图

Figure 3. Characterization of TiO2/CPCN electrodes: (a) front view of SEM; (b) SEM cross-sectional view; (c) Cross-sectional SEM-EDS elemental mapping

图4. 不同TiO2厚度下所获得的储能性能: (a) CV曲线; (b)光照与暗态下的电荷存储容量; (c) Clight/Cdark值; (d)光照与暗态下的库伦效率. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 4. Energy storage performance obtained under different TiO2 thicknesses: (a) CV curve; (b) Charge storage capacity under illumination and dark conditions; (c) Clight/Cdark values; (d) Coulombic efficiency under illumination and dark conditions. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

图5. 不同电极面积下所获得的储能性能: (a) CV曲线; (b) Nyquist图(插图为拟合值Rd和Rct值); (c)光生电荷存储容量对面积(Se)的影响; (d)每平方厘米光生电荷存储容量. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 5. Energy storage performance obtained under different electrode areas: (a) CV curve; (b) Nyquist plot (inset showing fitted values Rd and Rct); (c) Effect of photogenerated charge storage capacity on area (Se); (d) Photogenerated charge storage capacity per square centimeter. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

图6. 单个电池、2个并联电池和2个串联电池: (a) CV曲线; (b)工作状态下照片. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 6. Single cell, 2 parallel cells, and 2 series cells: (a) CV curve; (b) Photograph in working condition. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

图7. 不同面积单体电池串联组件: (a) CV曲线; (b)光生电荷存储容量. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 7. Serial modules with different areas: (a) CV curves; (b) Photogenerated charge storage capacity. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

图8. 不同面积单体电池并联组件: (a) CV曲线; (b)光生电荷存储容量; (c)质量比容量. 辐照条件为模拟AM 1.5太阳光(100 mW•cm-2)

Figure 8. Parallel components of single cells with different areas: (a) CV curves; (b) photogenerated charge storage capacity; (c) Mass specific capacity. The irradiation conditions were simulated AM 1.5 sunlight (100 mW•cm-2)

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