Preparation of three-dimensional coal tar pitch based porous carbon by α-Fe2O3 template for high performance supercapacitor
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摘要: 本研究以煤焦油沥青为原料,采用α-Fe2O3模板结合KOH活化法制备了三维结构分级多孔炭(HPCs),得到的HPC-3具有较高的比表面积(2003 m2/g),这是由于α-Fe2O3的占位(一定的中大孔)和KOH活化(丰富的微孔)协同作用导致的,其组装的双电层电容器在6 mol/L KOH电解液中具有最大的比电容(295 F/g)和优异的循环稳定性(10000次循环后,电容保持率高达97.8%)。同时,将其应用于EMIMBF4离子液体电解液,工作电压拓宽到3.6 V,能量密度高达60.0 (W·h)/kg。Abstract: In this paper, three-dimensional hierarchical porous carbons (HPCs) were prepared using coal tar pitch as raw material and α-Fe2O3 as template combined with KOH activation. The as-prepared HPC-3 showed large specific surface area (2003 m2/g), which was due to the synergistic effect of the occupation of α-Fe2O3 (certain mesopores and macropores) and KOH activation (abundant micropores). And the assembled electric double layer capacitor by HPC-3 exhibited the largest specific capacitance (295 F/g) and superior cycling stability (specific capacitance retention of 97.8% after 10000 cycles) in 6 mol/L KOH electrolyte. Meanwhile, the high working voltage (3.6 V) and energy density (60.0 (W·h)/kg) were obtained when it was applied to EMIMBF4 electrolyte.
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图 5 HPCs电极在6 mol/L KOH电解液中的电化学性能:(a)40 mA/g电流密度下的GCD曲线;(b)扫描速率为5 mV/s下的CV曲线;(c)不同电流密度对应的比电容图;(d)Nyquist图(插图为等效电路);(e)HPC-3电极的Ragone图和(f)HPC-3电极在2 A/g电流密度下的循环性能(插图为第一次和第10000次的GCD曲线)
Figure 5 Electrochemical performance of HPCs in 6 mol/L KOH electrolyte: (a) GCD curves at 40 mA/g; (b) CV curves at the scan rate of 5 mV/s; (c) Specific capacitance at various current densities; (d) Nyquist plots (inset was the equivalent circuit model); (e) Ragone plot of HPC-3 and (f) cycle stability of HPC-3 electrodes at 2 A/g (inset was the first cycle and the last cycle)
图 6 HPC-3电极在EMIMBF4离子液体电解液中的电化学性能:(a)扫描速率为10 mV/s不同电压窗口下的CV曲线;(b)不同扫描速率下的CV曲线;(c)不同电流密度下的GCD曲线和(d)Ragone图
Figure 6 Electrochemical performance of HPCs in EMIMBF4 ionic liquid electrolyte: (a) CV curves with different operation voltages at the scan rate of 10 mV/s; (b) CV curves at different scan rate; (c) GCD curves at various current densities and (d) Ragone plot
表 1 CTP的基本指标
Table 1 Basic index of CTP
Proximate analysis wad/% Ultimate analysis wdaf/% Softening poin t /℃ Mad Aad Vad FCad* C H N S O* 110 2.31 4.39 44.15 49.15 82.66 5.49 2.08 2.25 7.52 note: Mad: moisture of air drying basis; Aad: ash of air drying basis; Vad: volatile of air drying basis; FCad: fixed-carbon of air drying basis;
*: by subtraction表 2 HPCs的孔结构参数
Table 2 Pore structure parameters of HPCs
Sample SBET/(m2·g−1) Smicro/(m2·g−1) Smeco/(m2·g−1) vtotal/(cm3·g−1) vmicro/(cm3·g−1) dave/nm HPC-1 964 852 112 0.66 0.36 2.73 HPC-2 1663 1554 109 1.13 0.65 2.72 HPC-3 2003 1799 204 1.29 0.84 2.57 HPC-4 1013 854 159 0.82 0.41 3.25 note: SBET: specific surface area from multiple BET method; Smicro and vmicro: micropore specific surface area and volume calculated by t-plot method; Smeco: difference of SBET and Smicro; vtotal: total pore volume at p/p0 = 0.99; dave: average pore size 表 3 文献报道的CTP基多孔炭材料与本文工作的储能性能对比
Table 3 Electrochemical performance comparison of CTP-based porous carbon materials with previous reported reference
Raw material Specific capacitance / (F·g−1) Current densities / (A·g−1) Electrolyte Reference CTP 220.6 0.5 6 mol/L KOH [15] CTP 221 0.5 6 mol/L KOH [29] CTP 274 0.05 6 mol/L KOH [30] CTP 272 0.05 6 mol/L KOH [31] CTP/PAN 219 0.1 6 mol/L KOH [32] CTP 210 0.1 6 mol/L KOH [19] CTP 295 0.04 6 mol/L KOH this work CTP 240 0.5 6 mol/L KOH this work 表 4 HPCs的Rs和Rct拟合值
Table 4 Fitting value of the Rs and Rct of HPCs
Sample Rs / Ω Rct / Ω HPC-1 0.44 0.68 HPC-2 0.67 0.76 HPC-3 0.56 0.13 HPC-4 0.33 0.27 -
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