Novel, porous NiCo2O4 nanotubes (NCO-NTs) are prepared by a single-spinneret electrospinning technique followed by calcination in air. The obtained NCO-NTs display a one-dimensional architecture with a porous structure and hollow interiors. The effect of precursor concentration on the morphologies of the products is investigated. Due to their unique structure, the prepared NCO-NT electrode exhibits a high specific capacitance (1647 F g(-1) at 1 A g(-1)), excellent rate capability (77.3 % capacity retention at 25 A g(-1)), and outstanding cycling stability (6.4 % loss after 3000 cycles), which indicates it has great potential for high-performance electrochemical capacitors. The desirable enhanced capacitive performance of NCO-NTs can be attributed to the relatively large specific surface area of these porous and hollow one-dimensional nanostructures.
Electrochemical conversion reactions of transition metal compounds create opportunities for large energy storage capabilities exceeding modern Li-ion batteries. However, for practical electrodes to be envisaged, a detailed understanding of their mechanisms is needed, especially vis-à-vis the voltage hysteresis observed between reduction and oxidation. Here, we present such insight at scales from local atomic arrangements to whole electrodes. NiO was chosen as a simple model system. The most important finding is that the voltage hysteresis has its origin in the differing chemical pathways during reduction and oxidation. This asymmetry is enabled by the presence of small metallic clusters and, thus, is likely to apply to other transition metal oxide systems. The presence of nanoparticles also influences the electrochemical activity of the electrolyte and its degradation products and can create differences in transport properties within an electrode, resulting in localized reactions around converted domains that lead to compositional inhomogeneities at the microscale.
The structural and electrochemical properties of the mixed transition metallic oxides Zn1-xMnxFe2O4 nanofibers, which crystallize in a cubic spinel AFe2O4 structure, are investigated systematically with a gradual substitution of Zn by Mn. The crystal structural information studied by X-ray diffraction (XRD) depicts the formation of single phase spinel structure, while electron-dispersive X-ray spectroscopy (EDS) reveals the stoichiometric ratio between Zn and Mn. ZnFe2O4 exhibits a good capacity of ~532 mAh g(-1) at 50th cycle through the interbeneficial conversion reaction and alloy-dealloy mechanism, with a first discharge working voltage of ~0.83 V. Subsequently, the characteristic redox potential of each spinel is gradually reduced with the replacement of Mn. Furthermore, Zn0.3Mn0.7Fe2O4 demonstrates the highest capacity of ~612 mA h g(-1) at 50th cycle among the solid solution series. Ex situ characterization by high-resolution transmission electron microscope (TEM) and electron energy loss spectroscopy (EELS) is conducted to study the participation of Mn in the battery performance. This report represents an example of how the electrochemical performance could be flexibly adjusted by tuning the ratio of transition metals within the spinel.
A single-step fabrication of ZnSb nanostructures using template-free electrochemical deposition was developed. Results have indicated that ZnSb nanoflakes, nanowires, or nanoparticles with controlled composition could be obtained by adjusting the precursor concentration, applied voltage, and substrate type. The ZnSb nanostructures deposited on Cu foils were directly used as Li-ion battery anodes without the addition of any binder. Electrochemical analyses revealed that the interconnected ZnSb nanoflakes depicted high discharge capacities and a stable performance, which were better than that of ZnSb nanowires and nanoparticles. With an initial discharge capacity of 735 mA h/g and an initial Columbic efficiency of 85%, the ZnSb nanoflakes maintained a discharge capacity of 500 mA h/g with a Coulombic efficiency of 98% after 70 cycles at a current density of 100 mA/g (0.18 C). The ZnSb nanowires and nanoparticles showed a capacity of 190 and 40 mA h/g, respectively, after 70 cycles at the same current density. The improved performance of the interconnected ZnSb nanoflakes is attributed to their open structure, with a large surface area and small crystal grains, to facilitate the diffusion of Li ions and to buffer the large volume swings during the lithium intercalation process.
CaSnO₃ nanotubes are successfully prepared by a single spinneret electrospinning technique. The characterized results indicate that the well-crystallized one-dimensional (1D) CaSnO₃ nanostructures consist of about 10 nm nanocrystals, which interconnect to form nanofibers, nanotubes, and ruptured nanobelts after calcination. The diameter and wall thickness of CaSnO₃ nanotubes are about 180 and 40 nm, respectively. It is demonstrated that CaSnO₃ nanofiber, nanotubes, and ruptured nanobelts can be obtained by adjusting the calcination temperature in the range of 600-800 °C. The effect of calcination temperature on the morphologies of electrospun 1D CaSnO₃ nanostructures and the formation mechanism leading to 1D CaSnO₃ nanostructures are investigated. As anodes for lithium ion batteries, CaSnO₃ nanotubes exhibit superior electrochemical performance and deliver 1168 mAh g⁻¹ of initial discharge capacity and 565 mAh g⁻¹ of discharge capacity up to the 50th cycle, which is ascribed to the hollow interior structure of 1D CaSnO₃ nanotubes. Such porous nanotubular structure provides both buffer spaces for volume change during charging/discharging and rapid lithium ion transport, resulting in excellent electrochemical performance.
Single‐phase Na1.2V3O8 materials with single and hierarchical nanobelt morphologies were prepared by using a versatile electrospinning technique by altering the sintering profiles. On the basis of characterization by field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy, the formation mechanisms of products with tunable morphologies are discussed. The products obtained are employed as cathode materials for lithium‐ion batteries. Their electrochemical activities are demonstrated through galvanostatic cycling and cyclic voltammetry. The non‐agglomerated, single nanobelts with exposed (100) facets, which serve as channels for facile lithium diffusion, are capable of exhibiting higher maximum capacities of approximately 218 mAh g−1 compared to hierarchical nanobelts with a maximum capacity of approximately 197 mAh g−1 versus Li/Li+ at a current density of 200 mA g−1. Their associated reversible capacities are approximately 207 and 173 mAh g−1, respectively, after 100 cycles. Single nanobelts with individual belt‐like structures and preferred facet orientation also exhibit better rate capabilities.
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