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A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials

Gao Feng Xie Ya-qiao Zang Yun-hao ZHOU Gang QU Jiang-ying WU Ming-bo

高峰, 谢亚桥, 臧云浩, 周钢, 曲江英, 吴明铂. 功能集成策略制备孔结构可控的虾壳基多孔炭及超电应用[J]. 新型炭材料. doi: 10.1016/S1872-5805(21)60019-7
引用本文: 高峰, 谢亚桥, 臧云浩, 周钢, 曲江英, 吴明铂. 功能集成策略制备孔结构可控的虾壳基多孔炭及超电应用[J]. 新型炭材料. doi: 10.1016/S1872-5805(21)60019-7
Gao Feng, Xie Ya-qiao, Zang Yun-hao, ZHOU Gang, QU Jiang-ying, WU Ming-bo. A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials[J]. NEW CARBOM MATERIALS. doi: 10.1016/S1872-5805(21)60019-7
Citation: Gao Feng, Xie Ya-qiao, Zang Yun-hao, ZHOU Gang, QU Jiang-ying, WU Ming-bo. A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials[J]. NEW CARBOM MATERIALS. doi: 10.1016/S1872-5805(21)60019-7

功能集成策略制备孔结构可控的虾壳基多孔炭及超电应用

doi: 10.1016/S1872-5805(21)60019-7
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  • 中图分类号: TQ127.1+1

A sustainable strategy to prepare porous carbons with tailored pores from shrimp shell for use as the supercapacitor electrode materials

Funds: This work is supported by the NSFC (No. 51972059, 51901043), Scientific Research Foundation for Leading Scholars in Dongguan University of Technology (DGUT) (GB200902-31), Research start-up funds of DGUT (GC300501-072)
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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。
  • 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

    SampleSBET/m2 g-1SMic/m2 g-1SMec/m2 g-1SMic/SBET/%VTotal/cm3 g-1VMic/cm3 g-1VMic/VTotal/%Pore size/nm
    C-0% CaCO3117.60117.600.14003.0-5.1
    C-25% CaCO31371.81114257.881.50.640.4773.40.5-2.5
    C-50% CaCO3678.2154.1524.122.70.510.1633.40.95-5.5
    C-100%CaCO3390.250.3339.912.90.360.0185.31.5-5.0
    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.
    下载: 导出CSV

    Table  2.   The contents of N, C and O in the resultant carbons from XPS analysis.

    SampleXPS(wt.%)N-6[% (eV)]N-5[% (eV)]N-Q[% (eV)]N-X[% (eV)]O-I[% (eV)]O-II[% (eV)]
    CNO398.0399.7400.8402.0531.0532.2
    C-0% CaCO383.84.212.021.120.620.637.792.08.0
    C-25% CaCO388.03.68.417.818.335.029.025.874.2
    C-50% CaCO387.24.18.716.321.332.629.89.590.5
    C-100% CaCO386.94.09.115.120.034.630.319.280.8
    下载: 导出CSV

    Table  3.   Kinetic parameters of the C-X% CaCO3 electrodes.

    SampleRs (Ω)Rct (Ω)
    C-0% CaCO30.726.27
    C-25% CaCO30.051.55
    C-50% CaCO31.030.95
    C-100% CaCO30.623.01
    下载: 导出CSV

    Table  4.   Supercapacitor performance comparison of carbon materials.

    Raw MaterialSynthesis methodEnergy densities
    (Wh kg-1)
    Reference
    Shrimp shellsself-template and self-activator26.0This work
    Rice huskNaOH activation5.1Reference[40]
    CauliflowerKOH activation20.5Reference[43]
    CorncobKOH activation20.1Reference[41]
    White cloverZnCl2 activation13.1-25.0Reference[42]
    Shrimp shellsH3PO4 activation5.2Reference[23]
    Loofah spongeKOH activation16.1Reference[44]
    Wool fiberLiCl/KCl/KNO320.1Reference[45]
    下载: 导出CSV
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  • 收稿日期:  2021-01-01
  • 修回日期:  2021-01-01
  • 网络出版日期:  2021-02-05

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