The formation of uniform graphene-polyaniline hybrids using a completely miscible cosolvent that have an excellent electrochemical performance
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摘要: 石墨烯/聚苯胺复合材料的电化学性能很大程度上由其微观结构形貌和聚苯胺在石墨烯片层上的分布情况决定。在制备该复合材料时，两者的均相分布对于解决石墨烯片层的堆叠以及聚苯胺纳米结构的团聚至关重要。常见的聚苯胺/石墨烯均相复合材料制备方法，如逐层自组装或电化学原位聚合等，流程复杂、难以实现大规模生产。本文采用N, N-二甲基甲酰胺和水组成的互溶共溶剂成功地实现了石墨烯和聚苯胺的均相复合，通过共溶剂这一方式解决了上述所面临的问题。使用共溶剂的复合纤维展现出均相分布的微观结构，且聚苯胺均匀分布在石墨烯片层上，而相对比于只用水作为溶剂制备的复合纤维并未展现出均相复合的微观结构，使用共溶剂得到的复合纤维显示出优异的电化学性能。更重要的是通过共溶剂这一简单有效的策略，有望实现大规模生产两种成分均相分布且性能优异的石墨烯/聚苯胺复合材料。Abstract: The electrochemical properties of graphene-polyaniline (PANI) hybrids are largely determined by their microstructures and the distribution of PANI on the graphene network. Uniform hybridization of each component is critical to avoid the re-stacking of the graphene sheets and the agglomeration of PANI nanoassemblies during the use of the hybrids. Conventional strategies, such as layer-by-layer assembly or electrochemical in-situ polymerization, involve intricate procedures, making it difficult to achieve the large-scale production of the hybrids. We report a completely miscible cosolvent consisting of N, N-dimethylformamide and water that solves this problem and was used to produce graphene-PANI hybrid flexible fibers. It was found that the composite fiber had a homogeneous microstructure with PANI nanoassemblies uniformly distributed on the graphene sheets, and had outstanding electrochemical properties, much better than the counterpart fabricated using only water as the solvent. The work proposes a universal but simple strategy to achieve the mass production of graphene-PANI hybrids or similar materials with uniform hybridization of the two components.
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Key words:
- Graphene /
- Polyaniline /
- Cosolvent /
- Hybridization
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Figure 1. Photos of (a) GO suspensions, (b) PANI suspensions, (c) GO/PANI gel in a H2O/DMF cosolvent, and (d) the as-spun flexible GN/PANI composite fiber. (e) Raman spectra and (f) XRD patterns of PANI, pure GN fiber, and GN/PANI-CS fiber. (g) SEM image of GN/PANI-CS fiber showing the uniform diameter of the fiber. (h) Higher magnification SEM image and (i) TEM image of GN/PANI-CS fiber, further exhibiting the uniformly distributed PANI nanoneedles.
Figure 2. SEM images of as-prepared PANI dispersed by (a-c) H2O, (d-f) DMF, and (g-i) H2O/DMF cosolvent, followed by drying at 60 ºC.
Figure 3. (a) Stress-strain curves of pure GN fiber, GN/PANI-H2O, and GN/PANI-CS. (b) UV-vis spectra of PANI dispersed in H2O (black), DMF (red), and H2O/DMF cosolvent (blue). (c) CV curves at 5 mV s−1, (d) GCD profiles at 0.2 A g−1, (e) Nyquist plots and (f) Bode plots of GN/PANI-CS fiber supercapacitors with different mass ratios of GO to PANI.
Figure 4. (a) CV curves at 5 mV s−1, (b) GCD curves at 0.2 A g−1, (c) rate performance, (d) Nyquist plots, and (e) Bode plots of GN/PANI-H2O and GN/PANI-CS. (f) CV curves at different scan rates. (g) GCD profiles at various current densities of GN/PANI-CS. (h) Ragone plot of this work and other previously-reported literatures. (i) Cyclic performance at 1 A g−1 of GN/PANI-CS.
Figure 5. (a) Cartoons of devices of a single, two and three graphene/PANI-CS fiber supercapacitors connected in series or in parallel. (b) CV curves of a single, two, and three GN/PANI-CS fiber-based devices connected in parallel or in series at 2 mV s−1. (c) The GCD curves of single, two and three GN/PANI-CS fiber supercapacitors connected in parallel or in series at 0.1 A g−1. (d) Optical photo of a LED with a rated voltage of 1.5 V powered by a tandem device assembled by four fiber supercapacitors in series. (e) Cartoons of the fiber supercapacitor under bending conditions. (f) GCD profiles of a fiber supercapacitor at different bending angles.
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