Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

Higher-power supercapacitor electrodes based on mesoporous manganese oxide coating on vertically aligned carbon nanofibers.

A study on the development of high-power supercapacitor materials based on formation of thick mesoporous MnO2 shells on a highly conductive 3D template using vertically aligned carbon nanofibers (VACNFs). Coaxial manganese shells of 100 to 600 nm nominal thicknesses are sputter-coated on VACNFs and then electrochemically oxidized into rose-petal-like mesoporous MnO2 structure. Such a 3D MnO2/VACNF hybrid architecture provides enhanced ion diffusion throughout the whole MnO2 shell and yields excellent current collection capability through the VACNF electrode. These two effects collectively enable faster electrochemical reactions during charge-discharge of MnO2 in 1 M Na2SO4. Thick MnO2 shells (up to 200 nm in radial thickness) can be employed, giving a specific capacitance up to 437 F g(-1). More importantly, supercapacitors employing such a 3D MnO2/VACNF hybrid electrode illustrate more than one order of magnitude higher specific power than the state-of-the-art ones based on other MnO2 structures, reaching ∼240 kW kg(-1), while maintaining a comparable specific energy in the range of 1 to 10 Wh kg(-1). This hybrid approach demonstrates the potential of 3D core-shell architectures for high-power energy storage devices.

Atomic layer deposition of Al-doped ZnO/Al2O3 double layers on vertically aligned carbon nanofiber arrays.

High-aspect-ratio, vertically aligned carbon nanofibers (VACNFs) were conformally coated with aluminum oxide (Al2O3) and aluminum-doped zinc oxide (AZO) using atomic layer deposition (ALD) in order to produce a three-dimensional array of metal-insulator-metal core-shell nanostructures. Prefunctionalization before ALD, as required for initiating covalent bonding on a carbon nanotube surface, was eliminated on VACNFs due to the graphitic edges along the surface of each CNF. The graphitic edges provided ideal nucleation sites under sequential exposures of H2O and trimethylaluminum to form an Al2O3 coating up to 20 nm in thickness. High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy images confirmed the conformal core-shell AZO/Al2O3/CNF structures while energy-dispersive X-ray spectroscopy verified the elemental composition of the different layers. HRTEM selected area electron diffraction revealed that the as-made Al2O3 by ALD at 200 °C was amorphous, and then, after annealing in air at 450 °C for 30 min, was converted to polycrystalline form. Nevertheless, comparable dielectric constants of 9.3 were obtained in both cases by cyclic voltammetry at a scan rate of 1000 V/s. The conformal core-shell AZO/Al2O3/VACNF array structure demonstrated in this work provides a promising three-dimensional architecture toward applications of solid-state capacitors with large surface area having a thin, leak-free dielectric.