A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials
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摘要: 以虾壳作为集碳源、氮源、硬模板、活化剂四功能为一体的唯一原料，采用简单碳化的方法制备了孔结构可调控的氮掺杂多孔炭。采用醋酸溶液浸泡虾壳的方法使碳酸钙的含量在0-100%间变化，碳酸钙在低温时作为硬模板，而在高温时分解产生的氧化钙作为活化剂，进而实现多孔炭的比表面积在117.7-1137.0 m2 g-1，孔体积在0.14-0.64 cm3 g-1，微孔比例在0-73.4%间调控。将制备的多孔炭作为超级电容器电极材料，在KOH体系中，其最大比容量可达328 F g-1，能量密度和功率密度分别达到26.0 Wh kg-1，1470.9 W kg-1。本研究为低成本、绿色化制备生物质基氮掺杂多孔炭提供了可以借鉴的思路。Abstract: Highly efficient synthesis of nitrogen-doped carbons with different porous structures is reported using shrimp shell as the carbon and nitrogen source, and its CaCO3 component as the hard template and the activator. The content of CaCO3 in shrimp shell can be tuned easily in the range of 0-100% by leaching with an acetic acid solution for different times. CaO derived from decomposition of CaCO3 acts as the activator and template to tailor the pore sizes of the carbons. CO2 derived from decomposition of CaCO3 also plays an activating role. Their specific surface areas, pore volumes, ratios of micropore volumes to total pore volumes can be adjusted in the range of 117.6-1137 m2 g-1, 0.14-0.64 cm3 g-1, and 0-73.4%, respectively. When used as the electrodes of supercapacitor, the porous carbon obtained with a leaching time of 92 min exhibits the highest capacitances of 328 F g-1 at 0.05 A g-1 in a 6 M KOH electrolyte and 619.2 F g-1 at 0.05 A g-1 in a 1 M H2SO4 electrolyte. Its corresponding energy density at a power density of 1470.9 W kg-1 is 26.0 Wh kg-1. This work provides a low cost method for fabricating porous carbons to fulfill the high-value-added use of biomass.
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Figure 1. Schematic of N-doped carbon synthesis with tailored pore sizes from shrimp shell for supercapacitors.
Figure 2. (a) TGA curve of the shrimp shell in air and (b) The percentage of remaining CaCO3 of the shrimp shell with the variation times after leaching with 20 wt% HAC
Figure 3. SEM images of (a) raw shrimp shell, (b) shrimp shell after the complete removal of CaCO3 and (c) C-25% CaCO3 sample.
Figure 4. (a) N2 adsorption and desorption isotherms and (b) corresponding pore size distributions of C-0% CaCO3, C-25% CaCO3, C-50% CaCO3 and C-100% CaCO3 samples.
Figure 5. XPS spectra of C-X% CaCO3 (X=0, 25, 50, 100) samples: (a) C1s, (b) O1s and (c) N1s regions
Figure 6. Electrochemical characterizations of C-X% CaCO3(X=0, 25, 50, 100) samples measured in a three-electrolyte: (a) Cyclic voltammetry curves at a scan rate of 10 mV s-1, (b) Galvanostatic charge-discharge curves of these samples at a current density of 100 mA g-1, (c) Specific capacitances of carbon samples at different current densities, (d) Nyquist plots and (e) cycle performance of C-25% CaCO3 electrode measured at a current density of 1 A g-1, and the inset is the last 10 cycles of galvanostatic charge-discharge. All the above tests are conducted in a 6 M KOH solution.
Figure 7. Electrochemical characterizations of C-X% CaCO3 (X=0, 25, 50, 100) samples measured in a three-electrolyte: (a) CV curves at a scan rate of 10 mV s-1, (b) Specific capacitances at different current densities, (c) Galvanostatic charge-discharge curves of these samples at a current density of 100 mA g-1, (d) Nyquist plots and (e) cycle performance of C-25% CaCO3 electrode measured at a current density of 1 A g-1, and the inset is the last 10 cycles of galvanostatic charge-discharge. All the above tests are conducted in 1 M H2SO4 solution.
Figure 8. Electrochemical performance of C-100% CaCO3 and C-25% CaCO3 samples as supercapacitor electrodes in a two-electrode symmetric cell configuration in 6 M KOH: (a) CV curves at 10 mV s-1, (b) Galvanostatic charge-discharge curves at 50 mA g-1, (c) Nyquist plots, (d) Specific capacitances at different current density and (e) power density vs. energy density.
Table 1. Porous properties of the resultant carbons derived from shrimp shell
Sample SBET/m2 g-1 SMic/m2 g-1 SMec/m2 g-1 SMic/SBET/% VTotal/cm3 g-1 VMic/cm3 g-1 VMic/VTotal/% Pore size/nm C-0% CaCO3 117.6 0 117.6 0 0.14 0 0 3.0-5.1 C-25% CaCO3 1371.8 1114 257.8 81.5 0.64 0.47 73.4 0.5-2.5 C-50% CaCO3 678.2 154.1 524.1 22.7 0.51 0.16 33.4 0.95-5.5 C-100%CaCO3 390.2 50.3 339.9 12.9 0.36 0.018 5.3 1.5-5.0 Note: (a) SBET is the specific surface area obtained from BET method, (b) Smic is the microporous surface area calculated from t-plot method, (c) Smes is the mesoporous surface area from t-method external surface area (Smes=SBET-Smic) and (d) Vtotal is the total volume calculated at a relative pressure of 0.99. 
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Table 2. The contents of N, C and O in the resultant carbons from XPS analysis.
Sample XPS(wt.%) N-6[% (eV)] N-5[% (eV)] N-Q[% (eV)] N-X[% (eV)] O-I[% (eV)] O-II[% (eV)] C N O 398.0 399.7 400.8 402.0 531.0 532.2 C-0% CaCO3 83.8 4.2 12.0 21.1 20.6 20.6 37.7 92.0 8.0 C-25% CaCO3 88.0 3.6 8.4 17.8 18.3 35.0 29.0 25.8 74.2 C-50% CaCO3 87.2 4.1 8.7 16.3 21.3 32.6 29.8 9.5 90.5 C-100% CaCO3 86.9 4.0 9.1 15.1 20.0 34.6 30.3 19.2 80.8
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Table 3. Kinetic parameters of the C-X% CaCO3 electrodes.
Sample Rs (Ω) Rct (Ω) C-0% CaCO3 0.72 6.27 C-25% CaCO3 0.05 1.55 C-50% CaCO3 1.03 0.95 C-100% CaCO3 0.62 3.01
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Table 4. Supercapacitor performance comparison of carbon materials.
Raw Material Synthesis method Energy densities
(Wh kg-1)Reference Shrimp shells self-template and self-activator 26.0 This work Rice husk NaOH activation 5.1 Reference[40] Cauliflower KOH activation 20.5 Reference[43] Corncob KOH activation 20.1 Reference[41] White clover ZnCl2 activation 13.1-25.0 Reference[42] Shrimp shells H3PO4 activation 5.2 Reference[23] Loofah sponge KOH activation 16.1 Reference[44] Wool fiber LiCl/KCl/KNO3 20.1 Reference[45]
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