High-performance supercapacitors of porous carbon spheres synthesis from waste liquid
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摘要: 具有几何构型的球状结构可以减小电解质离子的传输距离，开发高比表面积、球形结构和制备工艺简单的多孔炭球，对于储能器件十分重要。以生产维生素C过程中产生的废液为原料，利用高温水热炭化和高铁酸钾（K2FeO4）为活化剂制备多孔炭球，并且详细研究了K2FeO4的量对所制备的多孔炭球的电化学性能影响。结果表明，所制备的样品呈现出球形结构且具有分级孔隙度（丰富的微孔和一定的中孔）的孔结构。在以6 mol/L KOH为电解液的三电极体系中，K2FeO4与焦质量比为2所得的多孔炭球（PCS-2）具有高的比表面积以及良好的电化学性能，在电流密度为0.5 A/g时，比电容高达323 F/g。以1-乙基-3-甲基咪唑四氟硼酸盐离子液体为电解液的对称型超级电容器中，K2FeO4与焦质量比为3所得的多孔炭球（PCS-3）能量密度高达47.2 W·h/kg，而且经过10000次循环后比电容保持率为89%。Abstract: The spherical structure can reduce the transmission distance of electrode ions. Preparation the porous carbon spheres with spherical structure, high specific surface area and simple method is critical for the electricity storage device. In this paper, the porous carbon spheres were obtained from waste liquid via hydrothermal treatment followed with K2FeO4 activation. The effect of K2FeO4 mass on the capacitive behavior of porous carbon spheres was investigated in detail. The results show that the samples obtained display spherical structure with hierarchical pore size distribution, which contain rich micropores and some mesopores. In the three system, the sample (PCS-2) with the mass ratio of K2FeO4 to char of 2 possesses high specific surface area and good electrochemical performance. In addition, the specific capacitance of PCS-2 is as high as 323 F/g at the current density of 0.5 A/g in 6 mol/L KOH electrolyte. The symmetric supercapacitor assembled with K2FeO4 to char of 3 electrode can deliver 47.2 W·h/kg energy density and maintain 89% capacitance after 10000 cycles in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid.
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Key words:
- porous carbon sphere /
- supercapacitors /
- waste liquid /
- specific capacitance /
- ionic liquid
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图 1 多孔炭球的（a）N2吸附-脱附等温线和（b）孔径分布
Figure 1 (a) Nitrogen adsorption-desorption isotherms and (b) pore size distributions of PCS-R
图 2 多孔炭球的（a）XRD谱图，（b）拉曼光谱谱图和（c）PCS-2的XPS的O 1s谱图
Figure 2 (a) XRD patterns, (b) Raman spectra of PCS-R and (c) O 1s of PCS-2
图 4 PCS-R电极在三电极体系中的电化学性质：（a）5 A/g下的恒电流充放电曲线，（b）扫描速率5 mV/s下的循环伏安曲线，（c）不同电流密度下的比电容和（d）PCS-2电极在不同电流密度下的恒电流充放电曲线
Figure 4 Electrochemical performances of PCS-R in a three-electrode system. (a) galvanostatic charge-discharge curves at 5 A/g, (b) cyclic voltammetry curves at 5 mV/s, (c) specific capacitances of PCS-R at different current densities and (d) galvanostatic charge-discharge curves of PCS-2 at various current densities
图 5 PCS-R电极在两电极体系中的电化学性质：（a）扫描速率为5 mV/s下不同电压窗口的循环伏安曲线，（b）5 mV/s下的循环伏安曲线，（c）200 mV/s下的循环伏安曲线，（d）PCS-R在不同电流密度下的比电容，（e）PCS-R在电流密度为0.5 A/g下的恒电流充放电曲线和（f）PCS-R的交流阻抗谱图
Figure 5 Electrochemical performances of PCS-R in a two-electrode system. (a) cyclic voltammetry curves at a scan rate of 5 mV/s under various voltage windows, (b) and (c) cyclic voltammetry curves at a scan rate of 5 mV/s and 200 mV/s, respectively, (d) comparison of specific capacitance at various current densities, (e) galvanostatic charging-discharging curves at a current density of 0.5 A/g and (f) Nyquist plots of the assembled devices
图 6 PCS-3电极的电化学性能：（a）不同电流密度下的恒电流充放电曲线，（b）不同扫描速率下的循环伏安曲线，（c）能量密度图和（d）PCS-3电极在5 A/g电流密度下的循环性能
Figure 6 Electrochemical performances of PCS-3 in a two-electrode system in EMIMBF4 electrolyte. (a) galvanostatic charge-discharge curves of the devices PSC-3 at various current density, (b) cyclic voltammetry curves at various scan rates from 5 to 200 mV/s, (c) ragone plot and (d) cycling performance
表 1 多孔炭球的孔结构参数
Table 1 Pore structure parameters of PCS-R
Sample SBET/(m2·g−1) vt/(cm3·g−1) dave/nm Smicro/(m2·g−1) Sext/(m2·g−1) vmicro/(cm3·g−1) vext/(cm3·g−1) v1−2/(cm3·g−1) v2−5/(cm3·g−1) w/% PCS-1 1219 0.60 1.96 1123 96 0.44 0.16 0.015 0.0052 38.8 PCS-2 1410 0.88 2.49 1174 236 0.49 0.39 0.082 0.023 35.2 PCS-3 1204 1.04 3.46 924 280 0.40 0.63 0.073 0.034 30.5 PCS-4 1146 0.86 3.00 959 187 0.41 0.45 0.074 0.033 27.4 note: SBET: specific surface area from multiple BET method; vt: total pore volume; dave: average pore diameter; Smicro and vmicro: micropore surface area and micropore volume from t-plot method, respectively; Sext and vext: the surface area and volume except the micropore surface area and micropore volume, respectively; v1−2 and v2−5: the pore volume of the pore size in the range of 1−2 nm and 2−5 nm are calculated based on DFT method, respectively; w: yield of activation 
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表 2 多孔炭球的元素分析
Table 2 Ultimate analysis of PCS-R
Sample Ultimate analysis wdaf/% C H N Oa PCS-1 89.2 1.3 1.7 7.8 PCS-2 88.5 1.4 1.9 8.2 PCS-3 88.1 1.4 1.9 8.6 PCS-4 87.3 1.5 2.0 9.2 a: by difference
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