富缺陷局部石墨畴结构的煤基碳材料构筑及其储钾特性研究

doi:10.6023/A24080253

摘要/Abstract

钾离子混合电容器(PIHCs)作为一种新型的电化学储能器件, 因其低成本和丰富的资源而成为大规模储能技术的候选者之一. 然而, 钾离子较大的半径导致其迁移速率缓慢, 并且反复脱嵌过程易引发材料的结构坍塌, 限制了器件的应用. 因此, 开发出低成本的碳材料以实现快速的离子扩散和良好的循环稳定性已成为PIHCs当前发展的重要挑战. 本工作以价格低廉的煤沥青为碳材料前驱, 采用高温催化限域的策略制备出具有局部石墨畴结构的N/P共掺杂煤基碳材料, 并对其储钾性能和反应动力学进行探究. 研究表明: N/P共掺杂引入了丰富的缺陷, 可为K⁺的吸附/脱附提供大量的边缘活性位点, 与此同时, 催化生长的纳米石墨畴有利于电子和离子快速的传输. 得益于煤基碳材料中的局部石墨畴、富活性氮和缺陷网络结构的协同作用, 优化的NPC-800负极展现了优异的储钾能力(2 A•g⁻¹电流密度下具有196.3 mAh•g⁻¹的比容量)和循环稳定性(稳定循环1000圈). 此外, 采用商业化活性炭(AC)正极和NPC-800负极构筑的PIHCs (AC//NPC-800)能实现101.4 Wh•kg⁻¹的高能量密度和长循环稳定性(1000圈), 展现出良好的应用前景. 鉴于煤沥青和钾资源的丰富低廉性, 该工作为低成本煤基碳材料在二次电池以及电化学电容器中的应用提供了一种可行性策略.

关键词: 钾离子混合电容器, 煤沥青, 碳材料, 富缺陷, 局部石墨畴

Potassium-ion hybrid capacitors (PIHCs), as a new type of electrochemical energy storage device, have become one of the candidates for large-scale energy storage technology due to their low cost and abundant resources. Carbon-based materials exhibit excellent conductivity, chemical stability, abundant availability, and low cost, making them become the most promising anode materials used for PIHCs. Notably, introducting local nanographitic domains into heteroatom-doped and defect-rich carbon-based materials is expected to provide sufficient reactive sites and structural stability, together with maintaining good electrical conductivity and ion diffusion rate. However, the larger radius of potassium ions leads to slow migration rates, and the repeated intercalation and deintercalation processes easily cause structural collapse of the active material, which limits the application of the devices. In this regard, developing low-cost carbon materials to achieve rapid ion diffusion and good cyclic stability has become an important challenge for the current development of PIHCs. Herein, the N/P co-doped coal-based carbon materials with local graphitic domain structure were prepared with a high-temperature catalytic confinement strategy by using cheap coal pitch as the carbon precursor, and their potassium storage properties and reaction kinetics were investigated. The study shows that N/P dual doping introduced abundant defects, which provide a large number of edge-active sites for the adsorption/desorption of K⁺. Meanwhile, the catalytically grown nanoscale graphitic domains facilitate rapid electron and ion transport. Thanks to the synergistic effect of the localized graphitic domains, rich active nitrogen, and defect network structure in the coal-based carbon material, the optimized NPC-800 anode exhibits excellent potassium storage capability (a specific capacity of 196.3 mAh•g⁻¹ at current density of 2 A•g⁻¹) and cycling stability (1000 cycles). In addition, the assembled PIHCs (AC//NPC-800) with commercial activated carbon (AC) cathode and the NPC-800 anode achieves a high energy density of 101.4 Wh•kg⁻¹ and long cycling stability (1000 cycles), demonstrating its promising application prospects. Given the abundance and low cost of coal tar pitch and potassium resources, this work provides a feasible strategy for the application of low-cost coal-based carbon materials in secondary batteries and electrochemical capacitors.

Key words: potassium-ion hybrid capacitors, coal pitch, carbon material, rich defect, local graphitic domain

引用此文

鞠治成, 封麒麟, 江野, 陈亚鑫, 庄全超, 邢政, 蒋江民. 富缺陷局部石墨畴结构的煤基碳材料构筑及其储钾特性研究[J]. 化学学报, 2024, 82(11): 1124-1133.

Zhicheng Ju, Qilin Feng, Ye Jiang, Yaxin Chen, Quanchao Zhuang, Zheng Xing, Jiangmin Jiang. Construction of Coal-based Carbon Materials with Rich Defect and Local Graphitic Domain Structures and Their Potassium Storage Properties[J]. Acta Chimica Sinica, 2024, 82(11): 1124-1133.

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图/表 10

图1. (a) NPC的制备流程示意图. (b, c) CTP、(d, e) NPC-700、(f, g) NPC-800和(h, i) NPC-900的扫描电子显微镜(SEM)图像

Figure 1. (a) The preparation process diagram of NPC. SEM images of (b, c) CTP, (d, e) NPC-700, (f, g) NPC-800, and (h, i) NPC-900, respectively

图2. (a) CTP和(b~d) NPC-800的TEM图像. (e) CTP、(f) NPC-700、(g) NPC-800和(h) NPC-900的HR-TEM图像. (i~m) NPC-800的EDS能谱

Figure 2. TEM images of (a) CTP and (b~d) NPC-800. HR-TEM images of (e) CTP, (f) NPC-700, (g) NPC-800, and (h) NPC-900, respectively. (i~m) EDS elemental mappings of NPC-800

图3. (a) NPC-700/800/900的XRD图像. (b) NPC-700/800/900微晶尺寸的计算示意图以及(c)相应的数值对比图. (d) NPC-700/800/900的拉曼光谱图以及(e)结构演变示意图

Figure 3. (a) XRD images of NPC-700/800/900. (b) The calculation diagram of microcrystal sizes and (c) corresponding numerical comparison diagram of NPC-700/800/900. (d) Ramna spectra of NPC-700/800/900 and (e) the schematic of structural evolution of NPC-700/800/900

图4. (a) NPC-700/800/900的N2吸附-脱附等温曲线和(b)对应的孔径分布图. NPC-800中(c) C 1s和(d) P 2p的分峰拟合图. (e) NPC-700/800/900中N 1s的分峰拟合图以及(f)对应活性N的占比

Figure 4. (a) N2 adsorption-desorption isotherms of NPC-700/800/900 and (b) corresponding pore size distributions. High-resolution XPS spectra of (c) C 1s and (d) P 2p of NPC-800. (e) High-resolution XPS spectra of N 1s of NPC-700/800/900 and (f) the corresponding percentage of active N

Sample	C (at%)	O (at%)	N (at%)	P (at%)
NPC-700	68.76	25.96	2.85	2.43
NPC-800	72.73	21.90	2.43	2.94
NPC-900	76.70	17.68	2.04	3.58

表1. 合成碳材料中C、O、N和P的含量占比

Table 1. The contents of C, O, N and P in synthesized carbon materials

图5. NPC-800的(a) CV曲线, (b) 0.05 A?g?1电流密度下的GCD曲线. (c)合成碳材料的倍率性能以及(d) NPC-800在不同电流密度下的GCD曲线. (e)碳材料在0.2 A?g?1电流密度下的循环性能. (f) NPC-800在0.2 A?g?1电流密度下的GCD曲线. (g)碳材料在1 A?g?1电流密度下的循环性能.

Figure 5. (a) CV curves, (b) GCD curves (0.05 A?g?1) of the NPC-800. (c) Rate performance of the synthesized carbon materials and (d) GCD curves of NPC-800 at different current densities. (e) Cycling performance of carbon samples at a current density of 0.2 A?g?1, and the (f) GCD curve (0.2 A?g?1) of the NPC-800. (g) Cycling performance of carbon samples at a current density of 1 A?g?1

图6. (a) NPC-700/800/900的GITT曲线和(b)对应的钾离子扩散系数. (c) NPC-700/800/900放电行为示意图

Figure 6. (a) GITT curves of NPC-700/800/900 and (b) corresponding potassium ion diffusion coefficients. (c) Schematic diagram of the discharge behaviors of NPC-700/800/900

图7. (a) NPC-800在不同扫速下的CV曲线. (b) NPC-700/800/900的拟合b值. (c) NPC-800在2 mV?s?1扫速下的表面电容贡献. (d) NPC-700/800/900在不同扫速下的电容贡献和(e) EIS图谱

Figure 7. (a) CV curves of NPC-800 at different sweep speeds. (b) The fitted b-values of NPC-700/800/900. (c) Surface capacitance contribution of NPC-800 at a sweep speed of 2 mV?s?1. (d) Capacitance contribution of NPC-700/800/900 at different sweep speeds and (e) EIS spectra

图8. (a) NPC-800的非原位XRD曲线以及(b) NPC-800在不同放电电位下的原位EIS图谱

Figure 8. (a) Ex-situ XRD of NPC-800 and the (b) In-situ EIS spectra of NPC-800 at different discharge potentials

图9. 钾离子电容器(NPC-800//AC)的(a) CV曲线、(b) GCD曲线、(c)能量-功率密度拉贡图和(d)循环性能

Figure 9. (a) CV curves, (b) GCD curves, (c) Ragone plots of energy-power density, and (d) cycling performance of assembled PIHCs (NPC-800//AC)

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