Preparation and electrochemical properties of triphenyl blue doped graphene/polypyrrole composite aerogels
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摘要: 将具有独特掺杂结构的聚吡咯(PPy)与丰富多孔结构的石墨烯(GE)气凝胶复合，可实现两种材料优势互补。通过一步水热法制备了曲利苯蓝(TB)掺杂GE/PPy复合气凝胶，采用SEM、FTIR、XRD、Raman和XPS对复合材料的形貌、化学结构、掺杂结构进行表征。结果表明，TB掺杂PPy/GE复合气凝胶呈现出三维多孔网络结构，复合气凝胶中氧化石墨烯(GO)被还原的同时，导电PPy被成功聚合，TB的引入有利于复合气凝胶掺杂水平的提高。电化学测试分析表明， TB掺杂浓度达到5 mmol·L−1时，复合气凝胶(TB-5/PPy-GO)可获得最高比电容(392 F·g−1)，10000次充/放电循环后，比电容保持率可达85%；将TB-5/PPy-GO、活性炭分别作为正、负极组装为非对称超级电容器，其在功率密度为400 W·kg−1时，能量密度高达35.89 W·h·kg−1，表现出良好的超电容特性。Abstract: The combination of polypyrrole (PPy) with a unique doping structure and graphene (GE) aerogel with a rich porous structure can realize the complementary advantages of the two materials. Triphenyl blue (TB) doped GE/PPy composite aerogel was prepared by one-step hydrothermal method. The SEM, FTIR, XRD, Raman spectroscopy and XPS were used to characterize the morphological structure, chemical structure, and doping structure of the composite electrode material. The results showed that TB doped GE/PPy composite aerogel provided three porous network structure. Conductive PPy can be successfully polymerized as graphene oxide (GO) was reduced in the composite hydrogel. Due to the introduction of TB, the doping level of the composite hydrogel has been increased. The electrochemical tests demonstrated that the prepared TB-5/PPy-GO (TB concentration of 5 mmol·L−1) aerogel exhibited superior specific capacitance of 392 F·g−1 at 1 A·g−1. The capacitance retention rate can reach 85% after 10 000 cycles. The hybrid device, which was assembled with TB-5/PPy-GO and active carbon as positive and negative electrode, respectively, demonstrated maximum energy of 35.89 W·h·kg−1 at 400 W·kg−1, suggesting its good supercapacitive performances.
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Key words:
- supercapacitor /
- polypyrrole /
- graphene /
- aerogl /
- triphenyl blue /
- electrochemical properties
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图 2 PPy-GO (a)、TB-1/PPy-GO (b)、TB-3/PPy-GO (c)、TB-5/PPy-GO (d)、TB-8/PPy-GO (e) 的SEM图像及TB-5/PPy-GO的EDS能谱图 ((f)~(i))
Figure 2. SEM images of PPy-GO (a), TB-1/PPy-GO (b), TB-3/PPy-GO (c), TB-5/PPy-GO (d), TB-8/PPy-GO (e) and EDS spectra of TB-5/PPy-GO ((f)-(i))
图 3 PPy-GO和TB/PPy-GO的FTIR图谱 (a)、XRD图谱 (b)、拉曼光谱图 (c)
Figure 3. FTIR spectra (a), XRD patterns (b), Raman spectra (c) of PPy-GO and TB/PPy-GO
图 4 样品的全谱图 (a)、PPy-GO (b)、TB-1/PPy-GO (c)、TB-3/PPy-GO (d)、TB-5/PPy-GO (e)、TB-8/PPy-GO (f) 的C1s XPS光谱图
Figure 4. Full spectrum of the sample (a), C1s XPS spectra of PPy-GO (b), TB-1/PPy-GO (c), TB-3/PPy-GO (d), TB-5/PPy-GO (e), TB-8/PPy-GO (f)
图 5 PPy-GO (a)、TB-1/PPy-GO (b)、TB-3/PPy-GO (c)、TB-5/PPy-GO (d)、TB-8/PPy-GO (e)的O1s XPS光谱图
Figure 5. O1s XPS spectra of PPy-GO (a), TB-1/PPy-GO (b), TB-3/PPy-GO (c), TB-5/PPy-GO (d), TB-8/PPy-GO (e)
图 6 PPy-GO (a)、TB-1/PPy-GO (b)、TB-3/PPy-GO (c)、TB-5/PPy-GO (d)、TB-8/PPy-GO (e) 的N1s XPS光谱图
Figure 6. N1s XPS spectra of PPy-GO (a), TB-1/PPy-GO (b), TB-3/PPy-GO (c), TB-5/PPy-GO (d), TB-8/PPy-GO (e)
图 7 PPy-GO、TB/PPy-GO (10 mV·s−1) (a)，TB-5/PPy-GO (b)的CV曲线；(c) PPy-GO、TB/PPy-GO的GCD曲线(1 A·g−1)；(d) TB-5/PPy-GO的GCD曲线；(e) PPy-GO、GBPs的EIS；(f) TB-5/PPy-GO的10 000圈循环稳定性测试(10 A·g−1)
Figure 7. CV curves of PPy-GO, TB/PPy-GO (10 mV·s−1) (a) and TB-5/PPy-GO (b); (c) GCD curves of PPy-GO, TB/PPy-GO (1 A·g−1); (d) GCD curves of TB-5/PPy-GO; (e) EIS of PPy-GO, TB/PPy-GO; (f) 10 000 cycle stability test of TB-5/PPy-GO (10 A·g−1)
t—Discharge time; −Z''—Imaginary impedance; Z'—Real impedance
图 8 TB-5/PPy-GO器件的CV (a)、GCD (b)、EIS (c)、10000圈循环稳定性测试(5 A·g−1)以及点亮LED电路板照片(d)
Figure 8. TB-5/PPy-GO devices CV (a) , GCD (b) , EIS curves (c) , 10000 cycle stability test (5 A·g−1) and photo of lighting up LED circuit board (d)
图 9 TB-5/PPy-GO器件不同电压下的CV曲线(10 mV·s−1) (a)，在0°、90°、135°、180°角度下弯折100次后CV (10 mV·s−1) (b)、GCD (1 A·g−1) (c)、EIS曲线 (d)
Figure 9. CV curves of TB-5/PPy-GO devices at different voltages (10 mV·s−1) (a), after bending 100 times at 0°, 90°, 135°, and 180° angles CV (10 mV·s−1) (b), GCD (1 A·g−1) (c), EIS curves(d)
图 10 TB/PPy-GO合成机制图
Figure 10. Schematic diagram of the synthesis mechanism of TB/PPy-GO
表 1 聚吡咯(PPy)/TB/氧化石墨烯(GO)复合气凝胶的原材料配比
Table 1. Ratios of the raw materials used in the polypyrrole (PPy)/TB/graphene oxide (GO) composite aerogels
Sample Py/mg GO/mg TB/(mmol·L−1) PPy-GO 140 56 0 TB-1/PPy-GO 140 56 1 TB-3/PPy-GO 140 56 3 TB-5/PPy-GO 140 56 5 TB-8/PPy-GO 140 56 8 Note: PPy-GO, TB-1/PPy-GO, TB-3/PPy-GO, TB-5/PPy-GO and TB-8/PPy-GO—Concentration of TB in the prepared composite aerogel as 0, 1, 3, 5, 8 mmol·L−1, respectively. 
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