纤维素基生物质多孔炭的制备及其超级电容器性能研究

doi:10.11949/0438-1157.20220437

摘要/Abstract

摘要：

以棉纤维素为原料，采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品，通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数，结果表明，4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能，其比表面积高达2433.8 m²·g^-1，在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1，在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量，具有良好的倍率性能；电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量，表明其具有长时工作的特性。

关键词: 纤维素, 生物质, 活化, 分级多孔炭, 电化学, 超级电容器

Abstract:

Using cotton cellulose as raw material, the hierarchical porous carbon (HPC) samples were prepared by pyrolyzing the mixture of magnesium nitrate, urea and cellulose. The specific surface area and pore structure of porous carbon were regulated by changing the calcination temperature and KOH activation treatment. By comparing the cyclic voltammetry curve, galvanostatic charge-discharge curve, specific capacity and other electrochemical parameters of the activated samples which were pre-calcined at three different temperatures, the results showed that 4AC@HPC800 sample had excellent electrochemical performance as the working electrode of supercapacitor, and its specific surface area reached 2433.8 m²·g^-1. The specific capacitance was as high as 234.7 F·g^-1 at the current density of 1 A·g^-1, and 207.6 F·g^-1 at the high current density of 10 A·g^-1, indicating that it had good rate performance. The electrode still presented a capacity of 196.1 F·g^-1 after 10000 cycles at the current density of 2 A·g^-1, indicating that it can work for a long time.

Key words: cellulose, biomass, activation, hierarchical porous carbon, electrochemistry, supercapacitor

中图分类号:

TB 34

陈健鑫, 朱瑞杰, 盛楠, 朱春宇, 饶中浩. 纤维素基生物质多孔炭的制备及其超级电容器性能研究[J]. 化工学报, 2022, 73(9): 4194-4206.

Jianxin CHEN, Ruijie ZHU, Nan SHENG, Chunyu ZHU, Zhonghao RAO. Preparation of cellulose-derived biomass porous carbon and its supercapacitor performance[J]. CIESC Journal, 2022, 73(9): 4194-4206.

图/表 13

表1 实验试剂及原料

Table 1 Reagents and raw materials

试剂	规格	生产厂家
脱脂棉毡	医用级	日本铃兰株式会社
六水合硝酸镁	AR(≥99%)	国药集团化学试剂有限公司
尿素	AR(≥99%)	上海阿拉丁生化科技股份有限公司
氢氧化钾	AR(≥85%)	国药集团化学试剂有限公司
聚四氟乙烯	60%(质量)分散液	上海阿拉丁生化科技股份有限公司

图1 生物质炭制备流程图

Fig.1 Flow chart of biomass carbon preparation

图2 HPC800活化前后的XRD谱图

Fig.2 XRD patterns of HPC800 before and after activation

图3 800℃煅烧温度下活化前后多孔炭的SEM图

Fig.3 SEM images of porous carbon before and after activation at 800℃

图4 煅烧温度与KOH活化对氮气等温吸脱附曲线与在NLDFT方法下的孔径分布的影响

Fig.4 The influence of calcination temperature and KOH activation on N2 isothermal absorption/desorption curves and pore size distribution under NLDFT method

表2 BET比表面积及孔容积特征

Table 2 BET specific surface area and pore volume

样品	BET SSA/(m²·g^-1)	a_total/(m²·g^-1)	a_ex/(m²·g^-1)	a_micro/(m²·g^-1)	V_0.95/(cm³·g^-1)	V_micro/(cm³·g^-1)	V_meso/(cm³·g^-1)
HPC1000	636.8	620.0	322.5	297.5	0.89	0.25	0.64
HPC900	828.7	825	507.9	317.1	1.03	0.26	0.77
HPC800	998.7	953.2	545.7	407.5	1.05	0.31	0.74
4AC@HPC1000	1223.7	1166.2	543.4	622.8	1.05	0.46	0.59
4AC@HPC900	2097.4	2050.4	968.0	1082.4	1.08	0.72	0.36
4AC@HPC800	2433.8	2429.0	1070.1	1358.9	1.10	0.78	0.32

图5 二电极测试在不同煅烧温度时：样品的循环伏安曲线[(a)、 (c)、 (e)]; 样品的恒电流充放电曲线[(b)、 (d)、 (f)]

Fig.5 Two electrode test at different calcination temperatures: cyclic voltammetry curves of samples [(a)、 (c)、 (e)]; constant current charge-discharge curves of samples [(b)、 (d)、 (f)]

图6 活化前样品的循环特性以及在高扫速、大电流密度下的性能比较

Fig.6 The cyclic characteristics of samples before activation and the performance comparison under high sweep speed and high current density

图7 活化后(KOH与粉体炭比例1∶4)：样品的循环伏安曲线[(a)、 (c)、 (e)]; 样品的恒电流充放电曲线[(b)、 (d)、 (f)]

Fig.7 After the activation (the ratio of KOH to carbon is 1∶4): cyclic voltammetry curves of samples [(a)、 (c)、 (e)]; constant current charge-discharge curves of samples [(b)、 (d)、 (f)]

图8 活化后样品的循环特性以及在高扫速、大电流密度下的性能比较

Fig.8 The cyclic characteristics of sample after activation and the performance comparison under high sweep speed and high current density

图9 活化后样品的交流阻抗谱图

Fig.9 AC impedance spectra of activated samples

图10 活化后样品的三电极测试

Fig.10 Three electrode test of activated samples

表3 对比不同生物质源和电解质下活性炭的比表面积和比容量

Table 3 Comparison of specific surface area and specific capacitance of various activated carbons derived from different biomass sources with different electrolytes

活性炭的生物质来源	电解液	比表面积 / (m²·g^-1)	最大比容量 / (F·g^-1)
荷秆^[28]	6 mol·L^-1 KOH	1022	248.5
花生壳^[29]	1 mol·L^-1 Na₂SO₄	890	239.88
米糠^[30]	3 mol·L^-1 KCl	1886	210
玉米壳^[31]	6 mol·L^-1 KOH	2349.89	140
废报纸^[32]	6 mol·L^-1 KOH	416	180
蔗渣^[33]	1 mol·L^-1 H₂SO₄	2871	300
玉米秸秆^[34]	H₂SO₄/PVA	1228	125
梧桐枯叶^[18]	3 mol·L^-1 KOH	1639.8	266
紫荆花^[35]	1 mol·L^-1 KOH	633.43	268
医用脱脂棉（本研究）	6 mol·L^-1 KOH	2433.8	283.3

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