Libo Deng

Supercapacitance from Cellulose and Carbon Nanotube Nanocomposite Fibers

Multiwalled carbon nanotube (MWNT)/cellulose composite nanofibers have been prepared by electrospinning a MWNT/cellulose acetate blend solution followed by deacetylation. These composite nanofibers were then used as precursors for carbon nanofibers (CNFs). The effect of nanotubes on the stabilization of the precursor and microstructure of the resultant CNFs were investigated using thermogravimetric analysis, transmission electron microscopy and Raman spectroscopy. It is demonstrated that the incorporated MWNTs reduce the activation energy of the oxidative stabilization of cellulose nanofibers from ∼230 to ∼180 kJ mol–1. They also increase the crystallite size, structural order, and electrical conductivity of the activated CNFs (ACNFs). The surface area of the ACNFs increased upon addition of nanotubes which protrude from the fiber leading to a rougher surface. The ACNFs were used as the electrodes of a supercapacitor. The electrochemical capacitance of the ACNF derived from pure cellulose nanofibers is demonstrated to be 105 F g–1 at a current density of 10 A g–1, which increases to 145 F g–1 upon the addition of 6% of MWNTs.

The effective young's modulus of carbon nanotubes in composites

A detailed study has been undertaken of the efficiency of reinforcement in nanocomposites consisting of single-walled carbon nanotubes (SWNTs) in poly(vinyl alcohol) (PVA). Nanocomposite fibers have been prepared by electrospinning and their behavior has been compared with nanocomposite films of the same composition. Stress transfer from the polymer matrix to the nanotubes has been followed from stress-induced Raman band shifts, which are shown to be controlled by both geometric factors such as the angles between the nanotube axis, the stressing direction and the direction of laser polarization, and by finite length effects and bundling. A theory has been developed that takes into account all of these factors and enables the behavior of the different forms of nanocomposite, both fibers and films, to be compared in different polarization configurations. The effective modulus of the SWNTs has been found to be in the range 530-700 GPa which, while being impressive, is lower than the generally accepted value of around 1000 GPa as a result of factors such as finite length effects and nanotube bundling. This value of effective modulus has, however, been shown to be consistent with the contribution of nanotubes to the 20% increase in Youngs modulus found for the nanocomposite films with a loading of only 0.2% of SWNTs. Hence a self-consistent method has been developed which enables the efficiency of reinforcement by nanotubes, and potentially other high-aspect-ratio nanoparticles, to be evaluated from stress-induced Raman bands shifts in nanocomposites independent of the specimen geometry and laser polarization configuration.

Strong Dependence of Mechanical Properties on Fiber Diameter for Polymer−Nanotube Composite Fibers: Differentiating Defect from Orientation Effects

We have prepared polyvinylalcohol-SWNT fibers with diameters from ∼1 to 15 μm by coagulation spinning. When normalized to nanotube volume fraction, V(f), both fiber modulus, Y, and strength, σ(B), scale strongly with fiber diameter, D: Y/V(f) ∝ D(-1.55) and σ(B)/V(f) ∝ D(-1.75). We show that much of this dependence is attributable to correlation between V(f) and D due to details of the spinning process: V(f) ∝ D(0.93). However, by carrying out Weibull failure analysis and measuring the orientation distribution of the nanotubes, we show that the rest of the diameter dependence is due to a combination of defect and orientation effects. For a given nanotube volume fraction, the fiber strength scales as σ(B) ∝ D(-0.29)D(-0.64), with the first and second terms representing the defect and orientation contributions, respectively. The orientation term is present and dominates for fibers of diameter between 4 and 50 μm. By preparing fibers with low diameter (1-2 μm), we have obtained mean mechanical properties as high as Y = 244 GPa and σ(B) = 2.9 GPa.

In situ polymerization of mechanically reinforced, thermally healable graphene oxide/polyurethane composites based on Diels–Alder chemistry

Covalently bonded graphene oxide/polyurethane (GO/PU) composites with significant reinforcement and thermally healable properties were developed via in situ polymerization based on Diels–Alder (DA) chemistry. The PU prepolymer was prepared with GO, 4,4-diphenylmethane diisocyanate, and poly(tetramethylene glycol) and blocked by using furfuryl alcohol firstly. Then the prepolymer was cross-linked by using bifunctional maleimide via DA chemistry. SEM shows that the GO was dispersed uniformly in the PU matrix. The DA and retro-DA reactions were characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry separately. Tensile tests showed that with the incorporation of 0.1 wt% of GO, the tensile modulus of GO/PU composites increased from 9.80 MPa to 21.95 MPa, and the tensile strength and elongation at break of the GO/PU composites increased by more than 367% and 210%, respectively. Furthermore, the composites had thermally healable ability which was inspected by using an atomic force microscope and the strain–stress test. The healing efficiency of 78% on average was achieved which was determined by the recovery of breaking stress and a healing mechanism was tentatively proposed. Therefore, the covalently bonded self-healing GO/PU composites could be used as smart materials and structural materials.

Toughening of epoxy matrices with reduced single-walled carbon nanotubes

Reduced single-walled carbon nanotubes (r-SWCNT) are shown to react readily at room temperature under inert atmosphere conditions with epoxide moieties, such as those in triglycidyl p-amino phenol (TGAP), to produce a soft covalently bonded interface around the SWCNT. The soft interface is compatible with the SWCNT-free cross-linked cured matrix and acts as a toughener for the composite. Incorporation of 0.2 wt % r-SWCNT enhances the ultimate tensile strength, toughness and fracture toughness by 32, 118, and 40%, respectively, without change in modulus. A toughening rate (dK(IC)/dwt(f)) of 200 MPa m(0.5) is obtained. The toughening mechanism is elucidated through dynamic mechanical analyses, Raman spectroscopy and imaging, and stress-strain curve analyses. The method is scalable and applicable to epoxy resins and systems used commercially.

ZIF-67-derived Co-NC@CoP-NC nanopolyhedra as an efficient bifunctional oxygen electrocatalyst

In this work, a highly efficient bifunctional electrocatalyst, Co/CoP embedded N-doped carbon (Co-NC@CoP-NC) nanopolyhedra, was derived by the thermal pyrolysis of ZIF-67 under an Ar atmosphere and a subsequent phosphidation process. The nanopolyhedra show excellent activity and stability for both the OER and ORR, which are attributed to the production of highly stable active CoP, and the intact protection of the Co by the N-doped carbon layers.

Coefficient of thermal expansion of carbon nanotubes measured by Raman spectroscopy

The coefficient of thermal expansion (CTE) of peapod-derived double-walled carbon nanotubes and their host empty single-walled carbon nanotubes (SWCNTs) was determined using Raman spectroscopy. This was performed by measuring the dependence of Raman band frequency of the nanotubes in epoxy resin matrix composites and considering the effects of both the strain and temperature on the Raman bands. Both types of nanotubes show positive thermal expansion at room temperature of around +2 × 10−5 K−1, and the CTE of the SWCNTs was unaffected by the introduction of the inner wall nanotubes. It was also demonstrated that the temperature-induced Raman band shifts can be used to determine both the CTE and glass transition temperature of the matrix polymers.

Electrochemical lithiation and delithiation of FeSb2 anodes for lithium-ion batteries

Abstract Iron antimonide, FeSb 2 , has been prepared by levitation melting. The electrochemical cycling behaviors of FeSb 2 were evaluated using lithium-ion model cell Li/LiPF 6 (EC+DMC)/FeSb 2 . It was found that the reversible capacity of FeSb 2 in the first cycle reached 507 mA h g −1 , and a reversible capacity of about 282 mA h g −1 was still maintained after 15 cycles. In our present work, we also found that the FeSb 2 /mesocarbon microbeads (MCMB) composite material possessed higher initial reversible capacity and better cycle life than pure FeSb 2 , which made it suitable for use as anode material in rechargeable lithium-ion batteries.

Strain-Driven and Ultrasensitive Resistive Sensor/Switch Based on Conductive Alginate/Nitrogen-Doped Carbon-Nanotube-Supported Ag Hybrid Aerogels with Pyramid Design

Flexible strain-driven sensor is an essential component in the flexible electronics. Especially, high durability and sensitivity to strain are required. Here, we present an efficient and low-cost fabrication strategy to construct a highly sensitive and flexible pressure sensor based on a conductive, elastic aerogel with pyramid design. When pressure is loaded, the contact area between the interfaces of the conductive aerogel and the copper electrode as well as among the building blocks of the nitrogen-doped carbon-nanotube-supported Ag (N-CNTs/Ag) aerogel monoliths, changes in reversible and directional manners. This contact resistance mechanism enables the hybrid aerogels to act as strain-driven sensors with high sensitivity and excellent on/off swithching behavior, and the gauge factor (GF) is ∼15 under strain of 3%, which is superior to those reported for other aerogels. In addition, robust, elastomeric and conductive nanocomposites can be fabricated by injecting polydimethylsiloxane (PDMS) into alginate/N-CNTs/Ag aerogels. Importantly, the building blocks forming the aerogels retain their initial contact and percolation after undergoing large-strain deformation, PDMS infiltration, and cross-linking of PDMS, suggesting their potential applications as strain sensors.

Electrochemical assessment of the interaction of dihydrogen phosphate with a novel ferrocenyl receptor.

A novel ferrocene-based amide has been synthesized by condensation reaction and characterized by (1)H NMR and UV-vis spectroscopies. The electrochemical properties and anion recognition properties of the ferrocene-based amide were investigated by the CV and UV-vis techniques. An interesting phenomenon was revealed by CV: a second oxidative peak, and the first oxidative peak decreased. Therefore, an effective dihydrogen phosphate recognition sensor is expected from this compound in the future.