十二烷基硫酸钠辅助制备高电容性能多孔碳

doi:10.6023/A21010007

摘要/Abstract

本工作通过一步水浴法制备高氮/氧含量密胺树脂(MF), 引入阴离子型表面活性剂十二烷基硫酸钠(SDS)改变聚合物的反应历程, 使进入SDS胶束中的三聚氰胺与甲醛在盐酸催化条件下进行聚合反应, 高温碳化后成功制备MF衍生多孔碳材料. 对MF衍生多孔碳材料分别进行了扫描电镜、比表面积等表征, 结果表明, 其具有多孔互穿网络结构, 比表面积高达387.86 m²?g^-1, 且孔径分布适宜(3.62 nm). 作为超级电容器(SCs)电极材料, 在1.0 A?g^-1下的比电容值为349.6 F?g^-1, 20.0 A?g^-1时(254.6 F?g^-1)仍能维持1.0 A?g^-1时73.0%的电容保持率, 倍率性能优异. 该样品在10.0 A?g^-1下循环15000次后的比电容值几乎没有衰减, 循环稳定性能优越. 此研究结果表明SDS可辅助提升MF衍生多孔碳材料的电容性能, 发展潜力巨大.

关键词: 密胺树脂, 十二烷基硫酸钠, 分级多孔结构, 高氮/氧含量, 高电容性能

Benefiting from the inducing effect of sodium dodecyl sulfate (SDS) during the polymerization process of melamine and formaldehyde, melamine resin (MF)-derived porous carbon materials with high nitrogen and oxygen content have been synthesized via an annealing-followed water bath method in this work. To study the effect of SDS on the synthesis and properties of MF-derived porous carbon materials, the microstructure and composition of as-prepared samples are characterized by scanning electron microscopy (SEM), nitrogen adsorption/desorption and X-ray photoelectron spectroscopy (XPS). It can be seen from SEM images that sample of the best additive amount (MFC-SDS30) has the interpenetrating network structure, which is conducive to the rapid transfer of electrons and electrolyte ions. Nitrogen adsorption/desorption isotherms indicate that all samples have large specific surface area (SSA) and more micropores/mesopores, which are caused by the pyrolysis of SDS at 700 ℃. MFC-SDS30 has the largest SSA (387.86 m²?g^-1) and a suitable pore size distribution (3.62 nm), which effectively improve the ion diffusion mobility and shorten the ion diffusion pathways. Interestingly, the XPS results show that MFC-SDS30 has high N atom content (15.5 at.%) and O atom content (6.5 at.%) without any additional doped treatment, so the abundant pseudocapacitance is contributed through the rapid N/O atoms redox reaction. Due to the above structural characteristics, MFC-SDS30 exhibits high specific capacitance value (C_sp) of 349.6 F?g^-1 at 1.0 A?g^-1, and the C_sp (254.6 F?g^-1) at 20.0 A?g^-1 still maintains 73.0% of that at 1.0 A?g^-1, showing good capacitive performance as electrode material for supercapacitors (SCs). The C_sp of MFC-SDS30 has almost no attenuation after 15000 cycles at 10.0 A?g^-1, which possesses good cycle stability. Besides, the maximum energy density of symmetrical SCs based on MFC-SDS30 is 9.2 Wh?kg^-1 at the power density of 250 W?kg^-1, and the energy density still reaches 4.0 Wh?kg^-1 at 5000 W?kg^-1, which is better than many reported carbon materials. Therefore, MF-derived porous carbon materials assisted by SDS can be a promising electrode material for SCs by means of a green and efficient method.

Key words: melamine formaldehyde resin, sodium lauryl sulfate, hierarchical porous structure, high nitrogen and oxygen content, high capacitive performance

引用此文

焦建超, 朱玉鑫, 彭晓薇, 金世航, 张云强, 李梅. 十二烷基硫酸钠辅助制备高电容性能多孔碳[J]. 化学学报, 2021, 79(6): 778-786.

Jianchao Jiao, Yuxin Zhu, Xiaowei Peng, Shihang Jin, Yunqiang Zhang, Mei Li. Preparation of High Capacitive Performance Porous Carbon Assisted by Sodium Dodecyl Sulfate[J]. Acta Chimica Sinica, 2021, 79(6): 778-786.

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图/表 8

图1. 样品的SEM照片: (a) MF-0, (b, c) MFC-0, (d) MF-SDS30, (e, f) MFC-SDS30

Figure 1. SEM images of samples: (a) MF-0, (b, c) MFC-0, (d) MF-SDS30 and (e, f) MFC-SDS30

图2. (a) XRD谱图, (b) Raman谱图, (c) FTIR谱图, (d) 热重曲线

Figure 2. (a) XRD spectra, (b) Raman spectra, (c) the FTIR spectra, (d) TGA curves of samples

图3. (a) 样品的氮气吸附/解吸等温线, (b) 样品的孔径分布曲线

Figure 3. (a) N2 adsorption/desorption isotherms, (b) pore size distribution for samples

Sample	S_BET^a/ (m²•g^-1)	S_micro^b/ (m²•g^-1)	S_meso/macro^c/ (m²•g^-1)	V_tot^d/ (cm³•g^-1)	V_micro^e/ (cm³•g^-1)	Average pore size/ nm
MFC-0	82.18	14.14	68.04	0.18	0.01	13.36
MFC-SDS20	321.50	241.20	80.30	0.21	0.19	2.58
MFC-SDS30	387.86	283.03	104.83	0.29	0.26	3.62
MFC-SDS40	251.05	231.47	19.58	0.14	0.12	2.23

表1. 系列样品的孔结构数据

Table 1. Pore textural data of samples

图4. 样品MFC-0的高分辨率XPS扫描(a) C 1s, (b) N 1s, (C) O 1s和样品MFC-SDS30高分辨率XPS扫描 (d) C 1s, (e) N 1s, (f) O 1s, (g~i)相对原子含量

Figure 4. High-resolution XPS scans for (a) C 1s, (b) N 1s, (c) O 1s of the MFC-0 and (d) C 1s, (e) N 1s, (f) O 1s of the MF-SDS30, (g~i) relative atom contents in the samples

Sample	C/at.%	N/at.%	O/at.%
MFC-SDS30	78.0	15.5	6.5
MFC-0	76.0	15.1	8.9

表2. 样品MFC-SDS30和MFC-0的元素原子比

Table 2. Elemental atomic ratio of MFC-SDS30 and MFC-0

图5. 样品的电化学性能图: (a) 扫描速率为10 mV?s-1时的CV曲线, (b) 电流密度为1.0 A?g-1时的GCD曲线, (c) Nyquist曲线, (d)不同电流密度下的Csp值. MFC-SDS30的电化学性能图: (e) 扫描速率为10~100 mV?s-1的CV曲线, (f) 在电流密度0.2~20.0 A?g-1下的GCD曲线

Figure 5. Electrochemical performance of samples: (a) CV curves at 10 mV?s-1, (b) GCD curves at 1.0 A?g-1, (c) Nyquist plots, (d) the Csp at different current densities. Electrochemical performance of MFC-SDS30: (e) CV curves at 10~100 mV?s-1, (f) GCD curves at 0.2~20.0 A?g-1

图6. 基于MFC-SDS30对称型SCs在2.0 mol?L-1 H2SO4中的电化学性能图: (a) 在10~100 mV?s-1下的CV曲线, (b) 在0.5~10.0 A?g-1时的GCD曲线, (c) Nyquist图, (d) 在不同电流密度下的Csp值, (e) 电极材料MFC-SDS30在10 A?g-1下的循环稳定性能, (f) 基于MFC-SDS30的对称型SCs的Ragone图(功率密度vs.能量密度)

Figure 6. Electrochemical performance of the MFC-SDS30 symmetric SCs in 2.0 mol?L-1 H2SO4: (a) CV curves at 10~100 mV?s-1, (b) GCD curves at 0.5~10.0 A?g-1, (c) Nyquist plots, (d) the Csp at different current densities, (e) cycle stability at 10 A?g-1of MFC-SDS30, (f) Ragone plot of symmetrical SCs based on MFC-SDS30 (power density vs. energy density)

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