Electrospun Nanotubular Titania and Polymeric Interfaces for High Energy Density Li-Ion Electrodes.

In the current study, for the first time, electrospinning of nanotubular structures was developed for Li-ion battery high energy density applications. For this purpose, titania-based nanotubular materials were synthesized and characterized. Before electrospinning with PVDF to obtain a self-standing electrode, the nanotubes were modified to obtain the best charge-transferring structure. In the current study, for the first time, the effects of various thermal treatment temperatures and durations under an Ar-controlled atmosphere were investigated for Li+ diffusion. Electrochemical impedance spectroscopy, cyclic voltammograms, and galvanostatic intermittent titration technique showed that the fastest charge transfer kinetics belongs to the sample treated for 10 h. After optimization of electrospinning parameters, a fully nanotube-embedded fibrous structure was achieved and confirmed by scanning electron microscopy and transmission electron microscopy. The obtained flexible electrode was pressed at ambient and 80 °C to improve the fiber volume fraction. Finally, the galvanostatic charge/discharge tests for the electrospun electrode after 100 cycles illustrated that the hot-pressed sample showed the highest capacity. The polymeric network enabled the omission of metallic current collectors, thus increasing the energy density by 14%. The results of electrospun electrodes offer a promising structure for future high-energy applications.

Practical Implementation of Magnetite-Based Conversion-Type Negative Electrodes via Electrochemical Prelithiation.

We report the performance of a conversion-type magnetite-decorated partially reduced graphene oxide (Fe3O4@PrGO) negative electrode material in full-cell configuration with LiNi0.8Co0.15Al0.05O2 (NCA) positive electrodes. To enable practical implementation of the conversion-type negative electrodes in full cells, the beneficial impact of electrochemical prelithiation on mitigating active lithium losses and improving cycle life is shown here for the first time in the literature. The initial Coulombic efficiency (ICE) of the full cells is improved from 70.8 to 91.2% by prelithiation of the negative electrode to 35% of its specific delithiation capacity. The prelithiation is shown to improve the surface passivation of the Fe3O4@PrGO electrodes, leading to less electrolyte reduction on their surface which is prominent from the significantly lowered accumulated Coulombic inefficiency values, lower polarization growth, and doubled capacity retention by the 100th cycle. The reduced surface reactions of the negative electrode by prelithiation also aids in reducing the extent of aging of the NCA positive electrode. Overall, the prelithiation leads to a longer cycle life, where a retained capacity of 60.4% was achieved for the prelithiated cells by the end of long-term cycling, which is 3 times higher than the capacity retention of the non-prelithiated cells. Results reported herein indicate for the first time that the electrochemical prelithiation of the Fe3O4@PrGO electrode is a promising approach for making conversion negative electrode materials more applicable in lithium-ion batteries.

Homogeneous growth of TiO2-based nanotubes on nitrogen-doped reduced graphene oxide and its enhanced performance as a Li-ion battery anode.

The pursuit of a promising replacement candidate for graphite as a Li-ion battery anode, which can satisfy both engineering criteria and market needs has been the target of researchers for more than two decades. In this work, we have investigated the synergistic effect of nitrogen-doped reduced graphene oxide (NrGO) and nanotubular TiO2 to achieve high rate capabilities with high discharge capacities through a simple, one-step and scalable method. First, nanotubes of hydrogen titanate were hydrothermally grown on the surface of NrGO sheets, and then converted to a mixed phase of TiO2-B and anatase (TB) by thermal annealing. Specific surface area, thermal gravimetric, structural and morphological characterizations were performed on the synthesized product. Electrochemical properties were investigated by cyclic voltammetry and cyclic charge/discharge tests. The prepared anode showed high discharge capacity of 150 mAh g-1 at 1 C current rate after 50 cycles. The promising capacity of synthesized NrGO-TB was attributed to the unique and novel microstructure of NrGO-TB in which long nanotubes of TiO2 have been grown on the surface of NrGO sheets. Such architecture synergistically reduces the solid-state diffusion distance of Li+ and increases the electronic conductivity of the anode.

The effect of pH on the interlayer distances of elongated titanate nanotubes and their use as a Li-ion battery anode.

Titanate nanotubes are promising materials for Li-ion battery anodes because of their special morphology and high specific surface areas. These titanates provide high rate capability and low volume expansion upon lithiation. More importantly, their tubular structure helps the transport of ions through the crystal. In this study, we synthesized elongated titanate nanotubes and modified their interlayer distances by changing the pH (2-13). For the structural characterization XRD, BET, SEM and TEM techniques were used. In addition, the effect of interlayer distance on energy capacity and rate capability was investigated. The highest interlayer distance was obtained at pH 10 and with decreasing pH, the interlayer distance dropped until reaching a pH value of 4. Conversely, the specific surface area reached its maximum value of 204 m(2) g(-1) at a pH of 4. Different from anatase (TiO2), titanate nanotubes had broad peaks in cyclic voltammograms suggesting a pseudocapacitive behavior. The sloping profiles of potential-capacity results also supported the pseudocapacitive property. For the titanate nanotubes obtained at pH 10, an initial discharge capacity of 980 mAh g(-1) was achieved. More importantly, titanate nanotubes showed exceptional rate capabilities and the capacities stayed almost constant at high current rates because of their elongated structure. It was found that the interlayer distance and the elongated structure play an important role in the electrochemical performance of the material.

Hydrothermal synthesis of nanostructured TiO2 particles and characterization of their photocatalytic antimicrobial activity.

Nanostructured titania particles were synthesized by using hydrothermal processing and the photocatalytic antimicrobial activities were characterized. Both sol-gel synthesized and commercial TiO2 (anatase) samples were processed with two step hydrothermal treatments, under alkaline and neutral conditions. Scanning Electron Microscope (SEM) images showed that alkaline treatment yields nanofibers and lamellar structured particles from the commercial anatase and sol-gel synthesized samples respectively. Further treatment of nanofibers and nanostructured lamellar particles with distilled water results with crystal growth and the formation of nano structured bipyramidal crystalline particles. The photocatalytic antimicrobial activities of the samples were determined against Escherichia coil under irradiation. It was observed that the samples treated under alkaline conditions have improved activity than the original anatase samples. Limited activity and resulting time lag in bacterial inactivation were observed for hydrothermally treated samples with distilled water. However, a post treatment comprising the UV irradiation in aqueous conditions enhanced the photocatalytic activity.