Facile preparation of pitch-derived carbon for high electrically conductive composites via carbon nanotube template
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摘要: 本研究以煤沥青为原料、多壁碳纳米管为结构导向剂，通过碳化制备了形貌和结构可控的煤沥青基碳膜，考察了多壁碳纳米管对导电填料结构及碳膜电热性能的影响规律。研究发现，多壁碳纳米管掺杂导致导电填料的晶格排列有序度增加、晶格间距减小和石墨化程度提高；多壁碳纳米管的引入提高了碳膜的载流子浓度，进而显著提高了其导电性。掺杂2%碳纳米管，可使煤沥青基碳膜的载流子浓度提高3.2倍、电阻降低67%；在5、10和15 V电压下，煤沥青基碳膜的发热温度分别可达44、88和165 ℃，相对未掺杂碳膜分别提高了7、22和70 ℃，显示出极大的应用前景。Abstract: Coal pitch, a byproduct of coal coking, is an ideal precursor for preparing conductive carbon fillers because of its rich aromatics and high yield of carbonization products. In this paper, coal pitch-based carbon materials with controllable morphology and structure were prepared by carbonization using coal pitch and multi-walled carbon nanotubes as raw material and structure-directing agent, respectively. The effect of carbon nanotubes on the structure and electrothermal properties of carbon materials was investigated. The results show that the doping of multi-walled carbon nanotubes results in an increase in the lattice arrangement order, a decrease in lattice spacing, and an increase in graphitization degree of conductive fillers, which leads to a significant increase in the carrier concentration of the carbon film and thus its conductivity. The doping of 2% carbon nanotubes can increase the carrier concentration of coal pitch-based carbon film by 3.2 times and reduce the resistance of coal pitch-based carbon film by 67%. At 5, 10 and 15 V, the heating temperature of the coal pitch-based carbon film can reach 44, 88 and 165 ℃, respectively, which is enhanced 7, 22 and 70 ℃ compared with the undoped carbon film, showing great application prospect.
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Key words:
- coal pitch /
- carbon film /
- carbon nanotube template /
- joule heating
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图 1 SEM照片：（a、b）PC；（c、d）PCNT2； TEM照片（e、f）PC；（g、h）PCNT2
Figure 1 SEM images of PC (a、b) and PCNT2 (c、d); TEM images of PC (e、f) and PCNT2 (g、h)
图 2 煤沥青基导电炭材料的（a）拉曼光谱谱图；（b）XRD谱图
Figure 2 Raman (a) and XRD (b) spectra of coal pitch-derived conductive carbon materials
图 3 煤沥青基导电碳填料的XPS 总谱图
Figure 3 Wide XPS (a), C 1s (b), O 1s (c), and N 1s (d) spectra of coal pitch-derived conductive carbon materials; Elemental contents (e); sp2 and sp3 carbon contents (f)
图 4 煤沥青基碳膜的载流子浓度（a）；载流子迁移率（b）和体积电阻率（c）
Figure 4 Carrier concentration (a), carrier mobility (b), and volume resistivity (c) of coal pitch-derived conductive carbon materials
图 5 煤沥青基碳膜的焦耳加热性能
Figure 5 Joule heating performance of coal pitch-derived conductive carbon materials at 5 (a), 10 (b), and 15 V (c)
图 6 PC和PCNT2所制备碳膜在不同电压下的升温、降温曲线
Figure 6 Temperature raising curves (a) and dropping curves (b) of carbon film obtained from PC under different voltage; Temperature raising curves (c) and dropping curves (d) of carbon film obtained from PCNT2 under different voltage
图 7 （a）PCNT2在15 V下的焦耳加热性能的稳定性测试；（b）磨损对PCNT2在15 V下的焦耳热性能的影响；（c）PC、PCG和PCNT2在15 V下的焦耳热性能
Figure 7 Joule heating stability of PCNT2 at 15 V (a); Effect of abrasion on Joule heating performance of PCNT2 at 15 V; Joule heating performance of PC, PCG, and PCNT2 at 15 V (c)
表 1 煤沥青基碳膜的附着性能
Table 1 Adhesion performance of coal pitch-derived carbon films
Sample Adhesion grade PC 2 B PCNT1 3 B PCNT2 3 B PCNT5 2 B SBR-PCNT2 5 B MMA-PCNT2 5 B 5B: Smooth of the edge of the incision and no peeling at the edge of the grid area; 4B: Small pieces peeling off at the intersection of the incision and the actual damage in the grid area not exceed 5%; 3B: Exfoliation of the edge of the incision with area greater than 5% but less than 15%; 2B: Exfoliation of the edge of the incision with area greater than 15% but less than 35% 
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表 2 煤沥青基碳膜的防腐性能
Table 2 Anticorrosion performance of coal pitch-derived carbon films
PC PCNT1 PCNT2 PCNT5 H2O NO NO NO NO Ethanol NO NO NO NO 1M NaCl NO NO NO NO 1M H2SO4 NO NO NO NO 1M HCl NO NO NO NO 1M NaOH NO NO NO NO
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