氮氧共掺杂多孔炭的制备及其锌离子混合超级电容器性能研究

曹恩德; 张苗苗; 刘海龙; 谢瑞伦; 田誉娇

doi:10.19906/j.cnki.JFCT.2022070

氮氧共掺杂多孔炭的制备及其锌离子混合超级电容器性能研究

doi: 10.19906/j.cnki.JFCT.2022070

安徽工业大学化学与化工学院煤清洁转化与高值化利用安徽省重点实验室, 安徽马鞍山 243032

基金项目: 安徽省自然科学基金（1708085QB33）和煤清洁转化与高值化利用安徽省重点实验室开放课题(CHV21-04、CHV22-02)资助

详细信息

通讯作者:
E-mail: ruilunxie@126.com

tyjiao@163.com

中图分类号: TM53
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出版历程
- 收稿日期: 2022-07-03
- 修回日期: 2022-08-06
- 录用日期: 2022-08-14
- 网络出版日期: 2022-09-05
- 刊出日期: 2023-04-15

Preparation of nitrogen and oxygen co-doped porous carbon and study on the performance of Zn-ion hybrid supercapacitors

School of Chemistry & Chemical Engineering, Anhui Key Laboratory of Coal Clean Conversion and High Valued Utilization, Anhui University of Technology, Ma'anshan 243032, China

Funds: The project was supported by Natural Science Foundation of Anhui Province (1708085QB33) and Anhui Province Key Laboratory of Coal Clean Conversion and High Valued Utilization (CHV21-04, CHV22-02).

摘要

摘要:
本研究以价格低廉、来源广泛的煤沥青作为炭前驱体、尿素作为氮源和模板、氢氧化钠作为活化剂，通过结合模板法与化学活化法成功制备了具有纳米片状结构的氮氧共掺杂的多孔炭材料。多孔炭电极在0.05 A/g时最大比容量高达255.5 mA·h/g，在电流密度为1 A/g时，放电比容量达到78 mA·h/g。经过12000次循环，容量保持率仍有72.4%，并且能量密度最高达到99.6 W·h/kg，展现出作为正极材料的巨大潜力。以煤沥青为原料制备的氮氧共掺杂多孔炭材料作为锌离子混合超级电容器的正极材料表现出了优异的电化学性能。
- 锌离子混合超级电容器 /
- 煤沥青 /
- 多孔炭 /
- 氮氧共掺杂 /
- 电极材料
Abstract:
In this study, nitrogen-oxygen co-doped porous carbon materials with nano-sheet structure were successfully prepared by template method and chemical activation method using coal pitch with low cost and abundant sources as carbon precursor, urea as nitrogen source and template, and sodium hydroxide as activator. The porous carbon electrodes exhibit a maximum specific capacity of 255.5 mA·h/g at 0.05 A/g and a discharge specific capacity of 78 mA·h/g at 1 A/g. Moreover, the porous carbon electrodes deliver about 72.4% capacitance retention after 12000 cycles and a high energy density of 99.6 W·h/kg, showing great potential as cathode material. The nitrogen-oxygen co-doped porous carbon materials prepared from coal pitch display an excellent electrochemical performance as cathode material for zinc ion hybrid supercapacitors.
- Zn-ion hybrid supercapacitor /
- coal pitch /
- porous carbon /
- nitrogen-oxygen co-doping /
- electrode material

HTML全文

FIG. 2214. FIG. 2214.

FIG. 2214. FIG. 2214.

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图 1 NO-PCM-x的制备流程示意图

Figure 1 Preparation process of NO-PCM-x

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图 2 原料煤沥青和NO-PCM-x的TG曲线

Figure 2 TG curves for raw coal pitch and NO-PCM-x

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图 3 （a）和（b）NO-PCM-5的SEM照片；（c） NO-PCM-5的元素分布；（d）和（e） NO-PCM-5的TEM照片

Figure 3 (a) and (b) SEM images of NO-PCM-5, (c) elemental distribution of NO-PCM-5, (d) and (e) TEM images of NO-PCM-5

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图 4 NO-PCM-x的（a）XRD谱图，（b）拉曼光谱谱图，（c）氮气吸附-脱附等温线，（d）和（e）孔径分布，（f）孔径分析

Figure 4 (a) XRD map, (b) Raman spectra, (c) nitrogen adsorption-desorption isotherms, (d) and (e) pore size distribution, (f) pore size analysis

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图 5 NO-PCM-5的XPS谱图

Figure 5 XPS maps of NO-PCM-5

(a): full; (b): C 1s; (c): N 1s; (d): O 1s

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图 6 （a）充放电电流为0.05 A/g时的GCD曲线对比，（b）NO-PCM-5在不同电流密度下的GCD曲线，（c）NO-PCM-x在不同电流密度下的放电比容量，（d）NO-PCM-x//3 mol/L ZnSO₄ (aq.)//Zn的Ragone图，（e）NO-PCM-x在1 A/g时的放电比容量和库伦效率

Figure 6 (a) GCD curve comparison plot at charge/discharge current of 0.05 A/g, (b) GCD curve of NO-PCM-5 at different current densities, (c) discharge specific capacity of NO-PCM-x at different current densities, (d) Ragone plot of NO-PCM-x//3 mol/L ZnSO₄ (aq.) //Zn, (e) discharge specific capacity and coulomb efficiency of NO-PCM-x at 1 A/g

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图 7 （a）NO-PCM-x//3 mol/L ZnSO₄ (aq.)//Zn储能系统示意图，（b）NO-PCM-x在2 mV/s时的CV曲线，（c）NO-PCM-5在2–50 mV/s的CV曲线，（d）在特定电位下的b值，（e）在不同扫描速率下电容控制和离子扩散控制对电容贡献的百分比，（f）NO-PCM-5在8 mV/s时的电容贡献

Figure 7 (a) Schematic diagram of NO-PCM-x//3 mol/L ZnSO₄ (aq.)//Zn energy storage system, (b) CV curves of NO-PCM-x at 2 mV/s, (c) CV curves of NO-PCM-5 at 2–50 mV/s, (d) b values at specific potentials, (e) percentage contribution of capacitance control and ion diffusion control to capacitance at different scan rates, (f) capacitance contribution of NO-PCM-5 at 8 mV/s

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图 8 （a）NO-PCM-x的阻抗谱图（内嵌图是NO-PCM-5的模拟电路图），（b）NO-PCM-x在阻抗图中低频区曲线的拟合

Figure 8 (a) Nyquist plot of NO-PCM-x (the inset shows the analogue circuit diagram of the NO-PCM-5), (b) the fitted line of NO-PCM-x

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表 1 原料煤沥青的工业分析和元素分析

Table 1 Proximate analysis and ultimate analyses of raw coal pitch

Proximate analysis w/% Ultimate analysis w_daf/%
M_ad A_d V_daf FC_daf^* C H N S O^*

0.08 1.00 55.80 43.12 91.34 4.01 1.03 0.43 3.19

*: by difference

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