基于结构调节碳材料的掺氮种类和含量及其超级电容器储能应用

doi:10.15541/jim20200498

无机材料学报 ›› 2021, Vol. 36 ›› Issue (7): 766-772.DOI: 10.15541/jim20200498

所属专题：【虚拟专辑】超级电容器(2020~2021)

基于结构调节碳材料的掺氮种类和含量及其超级电容器储能应用

孙鹏¹^,²(), 张绍宁¹^,³, 毕辉¹, 董武杰¹, 黄富强¹^,³^,⁴()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
2.中国科学院大学材料科学与光电技术学院, 北京 100049
3.上海科技大学物理科学与技术学院, 上海 200031
4.北京大学化学与分子工程学院, 稀土材料化学及应用国家重点实验室, 北京 100871

收稿日期:2020-08-27 修回日期:2020-10-20 出版日期:2021-07-20 网络出版日期:2020-11-05
通讯作者: 黄富强, 研究员. E-mail:huangfq@mail.sic.ac.cn
作者简介:孙鹏(1992-), 男, 博士研究生. E-mail:sunpeng@student.sic.ac.cn

Tuning Nitrogen Species and Content in Carbon Materials through Constructing Variable Structures for Supercapacitors

SUN Peng¹^,²(), ZHANG Shaoning¹^,³, BI Hui¹, DONG Wujie¹, HUANG Fuqiang¹^,³^,⁴()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Physical Science and Technology, ShanghaiTech University, Shanghai 200031, China
4. State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2020-08-27 Revised:2020-10-20 Published:2021-07-20 Online:2020-11-05
Contact: HUANG Fuqiang, professor. E-mail:huangfq@mail.sic.ac.cn
About author:SUN Peng (1992-), male, PhD candidate. E-mail:sunpeng@student.sic.ac.cn
Supported by:
National Key Research and Development Program of China(2016YFB0901600);National Natural Science Foundation of China(51972326);National Natural Science Foundation of China(51672295);National Natural Science Foundation of China(21871008);National Natural Science Foundation of China(51672301);Science and Technology Commission of Shanghai(18YF1427200);The Key Research Program of Chinese Academy of Sciences(QYZDJ-SSW-JSC013)

摘要/Abstract

摘要：

碳材料是极具潜力的超级电容器电极材料, 但是其容量较低。异质原子掺杂, 尤其是氮掺杂, 是大幅度提高碳材料电化学性能的有效方法。但是在碳材料中实现高含量的活性氮掺杂仍极具挑战。本研究通过Si-O-Si网络和氧化铝之间的相互作用成功调节碳材料的掺氮种类及其含量。除此之外, 通过调节前驱体组成, 碳材料的结构可以从珊瑚状转变为三维结构。在反应中, 氧化物中的氧原子可以和碳材料中氮原子成键, 氮原子不易逃离, 从而实现高含量氮掺杂(5.29at%@1000 ℃)。另一方面, 相互作用使碳材料孔体积增大(1.78 m³·g^-1)和孔径分布加宽(0.5~60 nm)。因此, 获得的富氮掺杂碳材料具有302 F·g^-1@1 A·g^-1的高容量和177 Fg^-1@120 A·g^-1的杰出倍率性能。此独特的固氮方法是一种有潜力的制备高性能超级电容器电极材料的策略。

关键词: 碳材料, 氮原子固定, 相互作用, 形貌设计, 超级电容器

Abstract:

Carbon materials are favorable for supercapacitors but suffer from insufficient capacitance. Heteroatom doping, especially nitrogen (N) doping, is an effective method to significantly improve the electrochemical performance, but it is still a big challenge to achieve high active nitrogen content in carbon materials. This work successfully tuned nitrogen species and content by interaction between Si-O-Si network and aluminum oxide. Besides, the structure of carbon materials varies from a coral-like network to three-dimensional structure by adjusting the precursor composition. Oxygen (O) in oxides bonds with N in carbon materials during the reaction, which makes it difficult to escape, achieving high nitrogen content of 5.29at% at 1000 ℃. On the other hand, the interaction empowers the carbon material with large pore volume of ~1.78 cm³·g^-1 and broad pore size distribution of 0.5-60 nm. Thus, the N-rich carbon material harvests high capacitance of 302 F·g^-1 at 1 A·g^-1 and excellent rate capability of 177 F·g^-1@120 A·g^-1. This unique nitrogen fixation method is a promising strategy for preparing high performance electrode materials of supercapacitors.

Key words: carbon material, nitrogen fixation, interaction, morphology design, supercapacitor

中图分类号:

O782

孙鹏, 张绍宁, 毕辉, 董武杰, 黄富强. 基于结构调节碳材料的掺氮种类和含量及其超级电容器储能应用[J]. 无机材料学报, 2021, 36(7): 766-772.

SUN Peng, ZHANG Shaoning, BI Hui, DONG Wujie, HUANG Fuqiang. Tuning Nitrogen Species and Content in Carbon Materials through Constructing Variable Structures for Supercapacitors[J]. Journal of Inorganic Materials, 2021, 36(7): 766-772.

图/表 18

Fig. 1 Schematic processing route from precursors to variable-structure carbon materials

Fig. 2 (a-d) SEM and (e-h) HRTEM images of (a, e) NC, (b, f) SiO-NC, (c, g) AlO-NC and (d, h) SiAlO-NC, and (i-l) energy dispersive spectroscopy (EDS) elemental mappings of SiAlO-NC

Fig. 3 (a) Nitrogen adsorption-desorption isotherms and (b) pore size distributions of NC, SiO-NC, AlO-NC, SiAlO-NC (after removing templates), N1s XPS spectra of (c) NC, SiO-NC, AlO-NC, SiAlO-NC (after removing templates) and (d) SiO-NC, AlO-NC, SiAlO-NC (without removing templates)

Table 1 BET and elemental parameters of samples

Sample	SSA /(m²·g^-1)	Pores volume /(cm³·g^-1)	N /at%	N-6 /at%	N-5 /at%
NC	440.78	0.07	1.42	0.21	0.03
SiO-NC	520.78	0.19	1.66	0.14	0.44
AlO-NC	980.35	0.68	3.52	0.78	1.75
SiAlO-NC	703.20	1.78	5.29	1.17	2.53

Fig. 4 (a) CV curves at 10 mV·s-1 and (b) galvanostatic charge/discharge (GCD) curves of NC, SiO-NC, AlO-NC, SiAlO-NC at 1 A·g-1 in three-electrode configuration; (c) CV curve of symmetric cell with SiAlO-NC, and (d) Ragone plots for SiAlO-NC and other nitrogen-carbon materials

Fig. S1 (a) Raman spectra and (b) XRD patterns of NC, SiO-NC, AlO-NC and SiAlO-NC

Fig. S2 C1s XPS spectrum of SiAlO-NC

Fig. S3 N1s XPS spectra of NC and SiAlO-NC at (a) 900 and (b) 1100 ℃

Fig. S4 (a) CV curve at 100 mV·s-1 and (b) GCD curve at 120 A·g-1 of SiAlO-NC in three-electrode configuration

Fig. S5 Specific capacitances calculated from GCD curves vs. current density for NC, SiO-NC, AlO-NC and SiAlO-NC

Fig. S6 Histograms of specific capacitance for SiAlO-NC at 1 A·g-1 vs. the heating temperature

Fig. S7 Cycling performance of SiAlO-NC electrode measured in three-electrode configuration

Fig. S8 CV curve of SiAlO-NC electrode measured in symmetric electrochemical cell at 100 mV·s-1

Fig. S9 GCD curves of SiAlO-NC electrode measured in symmetric electrochemical cells at (a) different current densities and (b) 40 A·g-1

Fig. S10 Nyquist plots over 0.01 to 105 Hz of NC, SiO-NC, AlO-NC and SiAlO-NC based on the fittings using equivalent Randles circuit model(inset) in three-electrode configuration

Fig. S11 Electrochemical performance of the SiAlO-NC sample(a) Capacitance versus discharge time, t1/2. Hollow symbols: CC test data, solid symbols: CV test data from 2 to 100 mV·s-1; Extrapolation of capacitance to t=0 gives a rate-independent capacitance; Instantaneous current of the SiAlO-NC sample at (b) 2 and (c) 50 mV·s-1, giving the shaded loop is the capacitive capacitance, and the region outside is the pseudocapacitance; (d) Fraction of capacitive capacitance Cc in total capacitance Ct

Table S1 Characteristic summary of NC and SiAlO-NC

Sample	N/at%	N-6/at%	N-5/at%	N-Q/at%	Sample	N/at%	N-6/at%	N-5/at%	N-Q/at%
NC (900 ℃)	2.81	1.54	0.82	0.45	NC (1100 ℃)	0.61	0.03	0.32	0.26
SiAlO-NC (900 ℃)	8.27	3.65	3.00	1.62	SiAlO-NC (1100 ℃)	4.33	1.61	1.27	1.45

Table S2 Comparison of the specific capacitances, rate capabilities and cycling performances for previously reported N-doped porous carbon materials

Carbon material	Specific capacitance /(F·g^-1)	Rate capability /(F·g^-1)	Cycling performance	Ref.
N-doped porous carbon	327 at 1 A·g^-1	200 at 20 A·g^-1	10000 cycles@100%	[2]
N/S co-doped porous carbon	272 at 1 A·g^-1	172 at 100 A·g^-1	5000 cycles at 5 A·g^-1@97.1%	[3]
N/O co-doped carbon	242 at 0.5 A·g^-1	132 at 20 A·g^-1	10000 cycles at 5 A·g^-1@97%	[4]
Graphene/N-rich carbon	229 at 1 A·g^-1	196 at 10 A·g^-1	10000 cycles at 2 A·g^-1@99.5%	[5]
N-doped carbon foam	280 at 1 A·g^-1	185 at 40 A·g^-1	10000 cycles at 5 A·g^-1@96.3%	[6]
N-doped tubular carbon	204 at 0.1 A·g^-1	173 at 10 A·g^-1	50000 cycles at 5 A·g^-1@91.5%	[7]
N-doped carbon microtube	309 at 1 A·g^-1	220 at 10 A·g^-1	10000 cycles at 1 A·g^-1@94%	[8]
N-doped porous carbon	292 at 1 A·g^-1	200 at 20 A·g^-1	10000 cycles at 1 A·g^-1@86%	[9]
N-doped carbon nanorod	271 at 0.5 A·g^-1	175 at 20 A·g^-1	10000 cycles at 5 A·g^-1@97%	[10]
3D porous carbon	261 at 0.5 A·g^-1	200 at 10 A·g^-1	5000 cycles at 1 A·g^-1@96%	[11]
N-doped porous carbon	250 at 1.0 A·g^-1	160 at 10 A·g^-1	3000 cycles at 1 A·g^-1@97.3%	[12]
N-doped carbon spheres	301 at 0.2 A·g^-1	210 at 5 A·g^-1	5000 cycles at 5 A·g^-1@100%	[13]
N-doped porous carbon	252 at 1.0 A·g^-1	189 at 15 A·g^-1	10000 cycles at 15 A·g^-1@94%	[14]
N-doped porous carbon	334 at 1.0 A·g^-1	215 at 20 A·g^-1	10000 cycles at 20 mV·s^-1@95.2%	[15]
3D graphene-like carbon	252 at 1.0 A·g^-1	168 at 50 A·g^-1	5000 cycles at 50 mV·s^-1@98%	[16]
SiAlO-NC	302 at 1 A·g^-1	218 at 20 A·g^-1	20000 cycles at 20 mV·s^-1@92%	This work
SiAlO-NC	302 at 1 A·g^-1	177 at 120 A·g^-1	20000 cycles at 20 mV·s^-1@92%	This work

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基于结构调节碳材料的掺氮种类和含量及其超级电容器储能应用

Tuning Nitrogen Species and Content in Carbon Materials through Constructing Variable Structures for Supercapacitors

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