N/S co-doped interconnected porous carbon nanosheets as high-performance supercapacitor electrode materials
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摘要: 如何采用无酸工艺合成高性能超级电容器（SCs）用多孔炭纳米片电极材料是一个大的挑战。本文报道了一种简便且无酸的由煤焦油沥青（CTP）构建N/S共掺杂相互连接的多孔炭纳米片（NS-IPCNs）的新方法。制备的NS-IPCN800具有相互连接的三维结构，这些三维结构由含有大量分级孔的二维炭纳米片组成。其中，丰富的微孔增加了离子吸附所需的活性位点，而短的中孔为离子传输提供了通道。此外，相互连接的三维结构为电子的快速传递提供了通道；掺杂的杂原子为NS-IPCNs电极提供了额外的赝电容。受益于这些优点， NS-IPCN800电极在6 mol L−1 KOH电解液中，在0.05 A g−1电流密度下的比电容达302 F g−1。另外，NS-IPCN800电容器在功率密度为25.98 W kg−1下其能量密度达9.71 Wh kg−1。更重要的是，NS-IPCN800电容器在10 000次循环充放电后电容保持率为94.2%，表现出优异的循环稳定性。这项工作为由CTP构建高性能储能装置用NS-IPCNs开辟了一种危害较小的策略。
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关键词:
- 煤焦油沥青 /
- N/S共掺杂相互连接的多孔炭纳米片 /
- 分级孔 /
- 超级电容器
Abstract: The synthesis of porous carbon nanosheets without acid treatment for high-performance supercapacitors (SCs) is difficult. We report the construction of N/S co-doped porous carbon nanosheets (NS-PCNs) from coal tar pitch (CTP), using Na2S2O3·5H2O as the sulfur source and K2CO3 as an activator, under flowing ammonia at high temperature. NS-IPCN800 prepared at 800 °C is composed of two-dimensional (2D) nanosheets with abundant pores and an interconnected 3D carbon skeleton. The abundant microspores increase the number of active sites for electrolyte ion adsorption and small mesopores act as channels for fast ion transmission. The 3D carbon skeleton provides paths for electron conduction. Heteroatom doping provides an additional pseudocapacitance for the NS-IPCN electrodes. As a result the NS-IPCN800 electrode has a high capacitance of 302 F g−1 at 0.05 A g−1 in a 6 mol L−1 of KOH electrolyte, and has a high energy density of 9.71 Wh kg−1 at a power density of 25.98 W kg−1. It also has excellent cycling stability with a capacitance retention of over 94.2% after 10 000 charge-discharge cycles. This work suggests an environmentally friendly way to produce NS-IPCNs from CTP for use as high-performance SC electrode materials. -
Figure 2. FESEM images of (a) NS-IPCN750, (b) NS-IPCN800, (c) NS-IPCN850, (d) N-IPCN800 and (e) S-IPCN800. TEM images of (f) NS-IPCN750, (g) NS-IPCN800 and (h) NS-IPCN850.
Figure 3. (a) Nitrogen adsorption/desorption isotherms of IPCNs, (b) Micropores and part mesopores size distribution curves of IPCNs.
Figure 5. (a) CV curves of IPCN electrodes at scan rate of 10 mV s−1 and (b) NS-IPCN800 electrode at scan rates of 2-500 mV s−1.
Figure 6. (a) GCD curves of IPCN electrodes at 1 A g−1 in 6 mol L−1 of KOH electrolyte, (b) GCD curves of NS-IPCN800 electrode at different current densities in 6 mol L−1 of KOH electrolyte, (c) Specific capacitance of IPCN capacitors at different current densities, (d) Ragone plots of IPCN capacitors, (e) Nyquist plots of IPCN capacitors, and (f) Cycle stability of NS-IPCN800 capacitor measured at 5 A g−1.
Table 1. Pore structure parameters of IPCNs.
Samples Dap (nm) SBET (m2 g−1) Vt (cm3 g−1) Vmic (cm3 g−1) NS-IPCN750 2.52 1019 0.85 0.38 NS-IPCN800 2.63 2000 1.31 0.60 NS-IPCN850 2.84 1977 1.45 0.45 N-IPCN800 2.21 1622 0.88 0.21 S-IPCN800 2.35 1682 0.98 0.28 Dap: average pore diameter; SBET: Brunauer–Emmett–Teller (BET) surface area; Vt: total pore volume; Vmic: micropores volume. 
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Table 2. Contents of C, O, N and S elements in IPCNs.
Samples C 1s (%) O 1s (%) N 1s (%) S 2p (%) O 1s C＝O (%) C―O (%) ―OH (%) NS-IPCN750 89.63 7.53 1.99 0.84 4.44 3.08 0.01 NS-IPCN800 93.95 4.63 0.99 0.43 2.41 2.21 0.01 NS-IPCN850 94.92 3.88 0.87 0.33 2.01 1.86 0.01 N-IPCN800 91.71 4.88 3.41 - 2.51 2.36 0.01 S-IPCN800 90.64 6.45 - 3.04 3.43 3.01 0.01
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Table 3. Comparison of the specific capacitance of NS-IPCN800 electrode.
Sample Electrolyte (mol L−1) Current density (A g−1) Cg (F g−1) Energy density (Wh kg−1) Ref. PB/rGO 1.0 Na2SO4 0.3 286 45.4 [34] GGI 6.0 KOH 0.5 301 9.1 [35] Carbon nanobowls 6.0 KOH 0.1 279 9.6 [36] ACS 6.0 KOH 1.0 208 9.2 [37] HPCNT 6.0 KOH 0.1 286 8.45 [38] SNPCNs 6.0 KOH 0.5 286 5.9 [39] RGO 1.0 Na2SO4 0.5 147.5 3.3 [40] HGNs 6.0 KOH 1.0 295 9.4 [41] NPS-HCS 6.0 KOH 0.5 274 8.4 [42] NS-IPCN800 6.0 KOH 0.05 302 9.71 This work
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