Nitrogen doped hollow porous carbon fibers derived from polyacrylonitrile for Li-S batteries
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摘要: 以聚丙烯腈（PAN）中空炭纤维为基体，通过KOH活化法制备了PAN中空多孔炭纤维用于锂硫电池正极材料基体。中空炭纤维经活化得到2491 m2·g−1的高比表面积和1.22 cm3·g−1的大孔隙体积。为了进一步提高电化学性能，使用水合肼对纤维前体进行了改性，以制备氮掺杂的中空多孔炭纤维。修饰后的纤维拥有1690 m2·g−1的比表面积，0.84 cm3·g−1的孔隙体积和8.81 at%的高氮含量。由于含氮基团可以增加纤维表面极性和吸附能力，所以在电流密度为1 C时，其起始比容量可以提升至到420 mAh·g−1。Abstract: Hollow porous carbon fibers for Li-S battery electrodes were prepared by the KOH activation of carbon prepared from hollow polyacrylonitrile fibers. The fibers had a high specific surface area of 2 491 m2·g−1, a large pore volume of 1.22 cm3·g−1 and an initial specific capacity of 330 mAh·g−1 at a current density of 1 C. To improve their electrochemical performance, the fibers were modified by treatment with hydrazine hydrate to prepare nitrogen-doped hollow porous carbon fibers with a specific surface area of 1 690 m2·g−1, a pore volume of 0.84 cm3·g−1 and a high nitrogen content of 8.81 at%. Because of the increased polarity and adsorption capacity produced by the nitrogen doping, the initial specific capacity of the fibers was increased to 420 mAh·g−1 at a current density of 1 C.
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Key words:
- Hollow-shaped carbon fibers /
- Activation /
- Modification /
- Li-S batteries
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Figure 1. SEM images of PAN hollow-shaped carbon fibers of (a) surface and (b) cross-section
Figure 2. (a) N2 adsorption/desorption isotherms and (b) pore size distribution obtained from DFT method for HSPCF-X (X=600, 700, 800, 900)
Figure 3. Cycling performance curves of HSPCF-X/sulfur composite electrodes at current density of 1 C (1 C=1675 mA g−1): (a) HSPCF-600, (b) HSPCF-700, (c) HSPCF-800 and (d) HSPCF-900
Figure 4. (a) SEM image of the surface of N-HSPCF, (b) Magnification of the white rectangle region in (a). (c) TEM image of N-HSPCF. Elemental maps of (d) nitrogen and (e) carbon corresponding to (a)
Figure 5. (a) N2 adsorption isotherms and (b) pore size distributions of HSPCF and N-HSPCF
Figure 6. (a) SEM image of CFs/S, elemental mapping of (b) sulfur, (c) carbon, (d) TG curve of CFs/S composite
Figure 7. (a) XPS full spectra of HSPCF and N-HSPCF. (b) Types of nitrogen-containing functional groups. N1s spectra of (c) HSPCF and (d) N-HSPCF
Figure 8. (a) CV curves of cells with HSPCF/S electrodes and N-HSPCF/S electrodes at 0.15 mV·s−1. (b) EIS spectra of cells with HSPCF/S electrodes and N-HSPCF/S electrodes from 0.01 to 100 kHz
Figure 9. Cycling performance, Coulombic efficiency and rate performance of (a,c) HSPCF/S electrodes and (b,d) N-HSPCF/S electrodes
Figure 10. SEM images of (a) HSPCF and (b) N-HSPCF electrode, insets of the cycled PP separators respectively
Table 1. Pore structure parameters of samples
Sample SBET(m2 g−1) Smicro(m2 g−1) Vtotal(cm3 g−1) VBJH(cm3 g−1) HSCF 0.19 - - - HSPCF-600 323.31 260.19 0.16 0.021 HSPCF-700 566.05 449.23 0.28 0.045 HSPCF-800 2490.98 992.42 1.22 0.407 HSPCF-900 2813.15 95.90 1.56 1.131 
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Table 2. Pore structure parameters of HSPCF and N-HSPCF
Samples SBET (m2·g−1) Smicro (m2·g−1) Vtotal (cm3·g−1) VBJH (cm3·g−1) HSPCF 2491 992 1.22 0.41 N-HSPCF 1690 1307 0.84 0.12
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Table 3. The content of surface nitrogen-containing functional groups for HSPCF and N-HSPCF
Sample XPS (at. %) Nitrogen functional group (%) C N O N-P N-X N-Q N-O HSPCF 83.55 4.15 12.31 - 40.29 55.16 4.55 N-HSPCF 80.80 8.81 10.39 19.25 53.50 26.75 -
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