skip to main content


Title: A comparative study of porous and hollow carbon nanofibrous structures from electrospinning for supercapacitor electrode material development
Co-axial electrospinning is an efficient technique to develop core-shell or hollow nanofibrous structures. In this study electrospun carbon nanofibers with three different morphologies, i.e. solid nanofibers with porous structure (P-ECNF), hollow nanofibers with solid wall (H-ECNF), and hollow nanofibers with porous wall (HP-ECNF) were developed through bicomponent electrospinning and co-axial electrospinning of polyacrylonitrile (PAN) and poly (methyl methacrylate) (PMMA) by varying proportion of the sacrificial PMMA. Through comparative electrochemical analyses, it is revealed that the primary factors for electrochemical performance, i.e. specific capacitance, of the electrospun carbon nanofibrous materials are mesopore volume and total pore volume. The hollow structure as well as ordered carbon structure and intact fiber structure also benefits electrolyte transfer and subsequent electrochemical performance but is secondary. Overall the porous carbon nanofibrous electrode material from electrospinning PAN/PMMA (50/50) solution (P-ECNF-50-50) outperformed those hollow and hollow-porous counterparts from co-axial electrospinning and demonstrated the largest specific capacitance due to the largest mesopore volume as well as the largest total pore volume. This electrode material also showed excellent cycling stability (without any loss of specific capacitance) after 3,000 cycles of charging and discharging. It even showed some increase of specific capacitance with cycling test due to its relatively large amount of micropores.  more » « less
Award ID(s):
1736173
NSF-PAR ID:
10317128
Author(s) / Creator(s):
Date Published:
Journal Name:
Surfaces and interfaces
Volume:
26
ISSN:
2468-0230
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Porous carbons are the active materials of choice for supercapacitor applications because of their power capability, long-term cycle stability, and wide operating temperatures. However, the development of carbon active materials with improved physicochemical and electrochemical properties is generally carried out via time-consuming and cost-ineffective experimental processes. In this regard, machine-learning technology provides a data-driven approach to examine previously reported research works to find the critical features for developing ideal carbon materials for supercapacitors. Here, we report the design of a machine-learning-derived activation strategy that uses sodium amide and cross-linked polymer precursors to synthesize highly porous carbons (i.e., with specific surface areas > 4000 m2/g). Tuning the pore size and oxygen content of the carbonaceous materials, we report a highly porous carbon-base electrode with 0.7 mg/cm2of electrode mass loading that exhibits a high specific capacitance of 610 F/g in 1 M H2SO4. This result approaches the specific capacitance of a porous carbon electrode predicted by the machine learning approach. We also investigate the charge storage mechanism and electrolyte transport properties via step potential electrochemical spectroscopy and quasielastic neutron scattering measurements.

     
    more » « less
  2.  
    more » « less
  3. null (Ed.)
    Lithium metal–selenium (Li–Se) batteries offer high volumetric energy but are limited in their cycling life and fast charge characteristics. Here a facile approach is demonstrated to synthesize hierarchically porous hollow carbon spheres that host Se (Se@HHCS) and allow for state-of-the-art electrochemical performance in a standard carbonate electrolyte (1 M LiPF 6 in 1 : 1 EC : DEC). The Se@HHCS electrodes display among the most favorable fast charge and cycling behavior reported. For example, they deliver specific capacities of 442 and 357 mA h g −1 after 1500 and 2000 cycles at 5C and 10C, respectively. At 2C, Se@HHCS delivers 558 mA h g −1 after 500 cycles, with cycling coulombic efficiency of 99.9%. Post-mortem microstructural analysis indicates that the structures remain intact during extended cycling. Per GITT analysis, Se@HHCS possesses significantly higher diffusion coefficients in both lithiation and delithiation processes as compared to the baseline. The superior performance of Se@HHCS is directly linked to its macroscopic and nanoscale pore structure: the hollow carbon sphere morphology as well as the remnant open nanoporosity accommodates the 69% volume expansion of the Li to Li 2 Se transformation, with the nanopores also providing a complementary fast ion diffusion path. 
    more » « less
  4. Abstract

    Designing 3D mechanically robust and high‐surface‐area substrates for uniform and high‐density deposition of metal–organic frameworks (MOFs) provide a promising strategy to enhance surface accessibility and application of these highly functional materials. Nanofibrous aerogel (NFA) with its highly porous self‐supported structure composed of interconnected nanofibrous network offers an ideal platform in this regard. Herein, a facile one‐pot strategy is introduced, which utilizes direct deposition of MOF on the nanofibrous surface of the NFAs. NFAs are synthesized using electrospun polyacrylonitrile/polyvinylpyrrolidone (PAN/PVP) polymer nanofibers containing zinc acetate (Zn(Ac)2), which are subjected to freeze drying and thermal treatment. The latter converts Zn(Ac)2to zinc oxide (ZnO), providing the sites for MOF growth while also adding mechanical integrity to the NFAs through cyclization of the PAN. Exposure of the NFA to the vapor‐phase of organic ligand, 2‐methylimidazole (2‐MeIm) enables in situ growth of zeolitic imidazolate framework‐8 (ZIF‐8) MOF on the NFA. ZIF‐8 loading on the NFAs is further improved by more than tenfold by synthesizing ZnO nanorods/protrusions on the nanofibers, which enables more sites for MOF growth. These findings underscore a significant advancement in designing MOF‐based hybrid aerogels, offering a streamlined approach for their use in diverse applications, from catalysis to sensing and water purification.

     
    more » « less
  5. The electrospinning of hydrocortisone/cyclodextrin complex nanofibers was performed in order to develop a fast-dissolving oral drug delivery system. Hydrocortisone is a water-insoluble hydrophobic drug, yet, the water solubility of hydrocortisone was significantly enhanced by inclusion complexation with hydroxypropyl-beta-cyclodextrin (HP-β-CyD). In this study, hydrocortisone/HP-β-CyD complexes were prepared in aqueous solutions having molar ratios of 1/1, 1/1.5 and 1/2 (hydrocortisone/HP-β-CyD). Highly concentrated aqueous solutions of HP-β-CyD (180%, w/v) were used for hydrocortisone/HP-β-CyD systems (1/1, 1/1.5 and 1/2) in order to perform electrospinning without the use of an additional polymer matrix. The turbidity of hydrocortisone/HP-β-CyD (1/1 and 1/1.5) aqueous solutions indicated the presence of some uncomplexed crystals of hydrocortisone whereas the aqueous solution of hydrocortisone/HP-β-CyD (1/2) was homogeneous indicating that hydrocortisone becomes totally water-soluble by inclusion complexation with HP-β-CyD. Nonetheless, the electrospinning of hydrocortisone/HP-β-CyD systems (1/1, 1/1.5 and 1/2) successfully yielded defect-free uniform nanofibrous structures. Moreover, the electrospinning process was quite efficient that hydrocortisone was completely preserved without any loss yielding hydrocortisone/HP-β-CyD nanofibers having the initial molar ratios (1/1, 1/1.5 and 1/2). The structural and thermal characterization of the hydrocortisone/HP-β-CyD nanofibers revealed that hydrocortisone was totally inclusion complexed with HP-β-CyD and was in the amorphous state in hydrocortisone/HP-β-CyD (1/2) nanofibers whereas some uncomplexed crystalline hydrocortisone was present in hydrocortisone/HP-β-CyD (1/1 and 1/1.5) nanofibers. Nevertheless, hydrocortisone/HP-β-CyD (1/1, 1/1.5 and 1/2) complex aqueous systems were electrospun in the form of nanofibrous webs having a free-standing and flexible nature. The hydrocortisone/HP-β-CyD (1/1, 1/1.5 and 1/2) nanofibrous webs have shown fast-dissolving behavior in water or when they were in contact with artificial saliva. Yet, the hydrocortisone/HP-β-CyD (1/2) nanofibrous web dissolved more quickly than the hydrocortisone/HP-β-CyD (1/1 and 1/1.5) nanofibrous webs due to the full inclusion complexation and the amorphous state of hydrocortisone in this sample. In short, the results suggest that polymer-free electrospun nanofibrous webs produced from hydrocortisone/HP-β-CyD could be quite applicable for fast-dissolving oral drug delivery systems. 
    more » « less