Effects of thermal treatment on the structural and capacitive properties of polyphenylsilane-derived porous carbon nanofibers
Introduction
Organic/inorganic composite materials have attracted a great deal of attention because of their potential use in many emergent applications, such as in gas storage and gas separation, and as catalytic support, specific adsorbents and electrodes in electric double-layer capacitors or Li-ion batteries [1], [2], [3], [4], [5], [6], [7]. They combine the advantages of the inorganic material (e.g., rigidity, thermal stability) and the organic polymer (e.g., flexibility, dielectric, ductility, and processability) [8]. Moreover, they usually also offer special properties of nanofillers leading to materials with improved properties [9]. Therefore, these hybrid nanocomposite systems may exhibit excellent characteristics in comparison to the properties of either of the pure components due to synergetic effects [10], [11]. Among the advanced organic/inorganic composite materials, one dimensional, polyacrylonitrile (PAN)-based, composite carbon nanofibers (CCNFs) have attracted much attention due to their high specific surface area, good chemical stability, and fabrication simplicity. A simple and low-cost approach for fabricating such nanofibers (NFs) is to utilize electrospinning to prepare carbon-precursor polymer composite NFs and subsequent thermal treatment at elevated temperatures to produce 1D carbon structures with suitable pore size distribution using a simple method without template carbons [12], [13], [14], [15], [16], [17], [18], [19].
In this work, organic-inorganic hybrid CCNFs with silicon oxynitride (SiOxNy) and silicon oxycarbide (SiOxCy) structure are prepared by one-step electrospinning and subsequent thermal treatment at different temperatures using polyphenylsilane (PPS) as an inorganic precursor. PPS represents a new class of polymer, which comprises σ-conjugated polymers with a one-dimensional silicon backbone and organic-substituted side chains having carbon-rich phenyl side groups. PPS have several advantages over other conductive polymers, making them very suitable for the preparation of polymer composites [20], [21], [22], [23]. Among the various organic precursors used to produce CNFs, PAN is considered the best candidate polymer due to its high carbon yield, its flexibility for tailoring the structure of the final CNF into the non-woven web, and its easy electrospinning and carbonization processes. Moreover, PAN-based CNFs can be used directly as electrode materials after thermal treatment, as has been realized with many other polymers [24], [25], [26]. Therefore, this work focuses on the effects of the PPS and variation in the carbonization temperature on the structure and electrochemical performance of the organic-inorganic hybrid CCNFs with SiOxNy and SiOxCy structures.
Section snippets
Materials and Fabrication
PAN, phenylsilane, and dimethylformamide (DMF) were purchased from Aldrich Chemical Co. (USA) and used as received. Electrospinning solutions were prepared by dispersing a given amount of PPS (30 wt% relative to PAN in a 10 wt% PAN solution) in DMF. The PPS (Mw = 1500∼2000 by GPC) was prepared by the catalytic dehydrogenative coupling of phenylsilane (Eq. 1) [22], [23]
The blend solution of PAN and PPS was electrospun into NFs using an electrospinning apparatus. The NFs were stabilized in air at
Results and Discussion
SEM images obtained at low and high magnification produced at carbonization temperatures of 800 °C and 1000 °C are presented in Fig. 1a-c. All of the fibers (Fig. 1a-c) exhibited long and continuous cylindrical morphologies. The average diameter of CNF-800 is about 300 nm and they have a smooth surface (Fig. 1a). PPS/CNF-800 and PPS/CNF-1000 became thinner and their morphologies displayed a wrinkled shape with white spots on the surface of the fiber, as shown in Fig. 1b-c, compared with CNF-800.
Conclusions
Porous CCNFs were obtained by simple thermal treatment of electrospun, PPS-incorporated, PAN-based NFs, thereby removing the need for a time-consuming activation step. The PPS was a key factor affecting the formation of micropores on the outer surface of the fibers, while the functional structures of SiOxCy and SiOxNy improved the performance in terms of the electrochemical capacitor and thermal stability. The organic-inorganic hybrid CCNF electrodes may be more suitable for high power
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